Identification of Lichen Substances (Huneck & Yoshimura 1996)

Siegfried Huneck and Isao Yoshimura
Identification of Lichen Substances

Springer
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Singapore
Tokyo
Siegfried Huneck Isao Yoshimura
Identification
of Lichen Substances
With 67 Figures
Springer
Dr. SIEGFRIED HUNECK
Fliederweg 34a
06179 Langenbogen/Saalkreis
Germany
Professor Dr. ISAo YOSHIMURA

Kochi Gakuen College
292 Asahitenjincho
Kochi 780
Japan
Cover photo by courtesy of Roman Turk. Photo showing various Lecidea and
Porpidia species on gneiss.
Formula: (+ )-Rhizocarpic acid
ISBN-13:978-3-642-8S24S-9
Library of Congress Cataloging-in-Publication Data
Huneck, S. (Siegfried), 1928-

Identification of lichen substances / S. Huneck, I. Yoshimura.
P. cm.
Includes bibliographical references (p. ) and index.
ISBN-13:978-3-642-85245-9 e-ISBN-13:978-3-642-85243-5
DOl: 10.1007/978-3-642-85243-5
1. Lichen products-Handbooks, manuals, etc. 2. Lichens-
Analysis-Handbooks, manuals, etc. I. Yoshimura, l. (Isao)
II. Title.
QK581.H86 1996
S89.1-dc20
96-3927
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are liable for prosecution under the German Copyright Law.
Springer-Verlag Berlin Heidelberg ~996

Softcover reprint of the hardcover 1st edition 1996
Product Liability: The publisher can give no guarantee for information about drug dosage and application
thereof contained in this book. In every individual case the respective user must check its accuracy by consulting
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Dedicated
to our friends John A. Elix,
Benno Feige, Wolfgang Steglich
and Raffaele Tabacchi
Acknowledgments
We are grateful to Prof. Dr. J.A. Elix (Canberra), Prof. Dr. C. Leuckert
(Berlin), Prof. Dr. R. Tabacchi (Neuchatel) and Dr. P.A. Cohen
(Vancouver) for providing reprints and unpublished data, and to Dr.
H.T. Lumbsch (Essen) for checking the names of the lichens. S. Huneck
thanks his wife Ruth for manifold help in preparing the manuscript and
the Fonds der Chemischen Industrie (Frankfurt/Main) for financial
support.
S. HUNECK
1. YOSHIMURA
Contents
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Short History of the Study of Lichen Substances. . . . . . . . 1

1.2 General Meaning of Lichen Substances
and Their Use in Past and Present Time. . . . . . . . . . . . . . 3
1.2.1 Biological Activities of Lichen Substances. . . . . . . . . . . . 3
1.2.2 Use of Lichens in Folk Medicine. . . . . . . . . . . . . . . . . . . 4
1.2.3 Lichens as Raw Material for Dyes . . . . . . . . . . . . . . . . . . 5
1.2.4 Lichens as Basic Material for Perfume. . . . . . . . . . . . . . . 5
1.2.5 The Biological Meaning of Lichen Substances. . . . . . . . . 5
1.2.6 Lichens as Biomonitors . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.7 Lichens as Biodeterioration . . . . . . . . . . . . . . . . . . . . . . 6
1.2.8 Chemotaxonomy of Lichens ..................... 6
1.3 Cultur~ of Lichens and Their Symbionts . . . . . . . . . . . . . . 9
2 Identification of Lichen Substances. . . . . . . . . . . . . . . . . . 11
2.1 Extraction and Purification of Lichen Substances. . . . . . . 11

2.2 Melting Point. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3 Colour Reactions and Other Reactions
for the Identification of Lichen Substances. . . . . . . . . . . . 13
2.4 UV Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.1 Depsides......................................... 17
2.4.2 Depsidones....................................... 17
2.4.3 y-Lactones....................................... 17
2.4.4 Chromones and Xanthones . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.4.5 Dibenzofuranes .................................. . 18
2.4.6 Pulvinic Acid Derivatives .......................... . 18
2.4.7 Quinones ....................................... . 18
2.5 IR Spectroscopy .................................. . 18
2.6 NMR Spectroscopy ... " ........................... . 19
2.6.1 lH-NMR Spectroscopy ............................ . 19
2.6.2 13C-NMR Spectroscopy ............................ . 20
2.7 Mass Spectrometry ............................... . 22
2.8 Optical Rotation .......................... <' 28
X Contents
2.9 Optical Rotatory Dispersion (ORD) and

Circular Dichroism (CD) .......................... . 28
2.10 Microcrystallization .............................. . 47
2.11 Thin Layer Chromatography ....................... . 47
2.12 High Performance Liquid Chromatography (HPLC) .... . 51
2.13 Gas Liquid Chromatography (GLC) ................. . 107
2.14 X-Ray Analysis .................................. . 109
2.15 Laser Microprobe Mass Spectrometry (LAMMA) ...... . 109
2.16 Derivatization ................................... . 109
2.17 Cleavage of Depsides ............................. . 112
3 Data of Lichen Substances ......................... . 125

3.1 General Remarks and Abbreviations of the Data ....... . 125
3.2 N-Containing Compounds ......................... . 126
3.3 P-Containing Compounds ......................... . 130
3.4 S-Containing Compounds ......................... . 131
3.5 Polyols, Monosaccharides, Carbohydrates ............ . 131
3.6 Aliphatic and Cycloaliphatic Compounds ............ . 136
3.6.1 Neutral Compounds .............................. . 136
3.6.2 Acids ........................................... . 141
3.7 Aromatic Compounds ............................ . 155
3.7.1 Monocyclic Aromatic Compounds .................. . 155
3.8 Quinones ....................................... . 164
3.8.1 Benzoquinones .................................. . 164
3.8.2 Naphthaquinones and bis-Naphthaquinones .......... . 164
3.8.3 Anthraquinones, Anthrones, bis-Anthraquinones
and bis-Anthrones ............................... . 168
3.8.4 Biphenylquinones ................................ . 183
3.8.5 Terphenylquinones ............................... . 184
3.8.6 Phenanthrenequinones ............................ . 184
3.8.7 Perylenequinones ................................ . 185
3.9 Chromanes and Chromones ....................... . 185
3.10 Xanthones and bis-Xanthones ...................... . 190
3.11 Dibenzofuranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
3.12 Diphenylether.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
3.13 Biphenyls.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.14 Diphenylmethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.15 Nostoclides.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.16 Depsides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
3.16.1 Didepsides ............................... '. . . . . . . . 237
3.16.2 Tri- and Tetra-Depsides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
3.16.3 Benzyldepsides....... . . . . . . . . . . . . . . . . . . . . . . . . . . .. 311
3.17 Depsidones... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Contents X
3.18 Depsones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

3.19 Naphthopyranes... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.20 Terpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.20.1 Monoterpenoids.................................. 356
3.20.2 Sesquiterpenoids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 359
3.20.3 Diterpenoids..................................... 360
3.20.4 Sesterterpenoids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
3.20.5 Triterpenoids..................................... 362
3.20.6 Steroids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 388
3.20.7 Carotenoids...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
3.21 Pulvinic Acid Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . .. 399
3.22 Cleavage Products of Depsides and Depsidones . . . . . . . . 403
Literature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Addenda .............................................. 475
Subject Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479

1 Introduction
1.1 Saxony, Germany, died 1917 at Feuerbach near

Short History of the Study Stuttgart), who published 18 papers on lichen
of Lichen Substances substances in the period between 1861 and 1905
and wrote an article on Flechtenstoffe in the
Lichens - symbiotic organisms of fungi and 1912 edition of Abderhalden's Biochemisches
algae - contain a great number of organic Handlexikon.
compounds, the so-called lichen substances The lichen substances first known in their
which are more or less typical of this group structure were vulpinic acid (Spiegel 1883) and
of cryptogames. The lichen substances com-
prise quite different classes of compounds
like amino acid derivatives, sugar alcohols,
aliphatic acids, 'Y-, 0- and macrocyclic lactones,
mono cyclic aromatic compounds, quinones,
chromones, xanthones, dibenzofuranes, de-
psides, depsidones, depsones, terpenoids, ste-
roids and carotenoids. This multitude of
compounds made the study of their chemistry
attractive from the early times of organic chem-
istry. Bebert (1831) isolated vulpinic acid in
1831, Alms (1832) picrolichenic acid in 1832,
and Knop (1844) usnic acid in 1844. Gmelin
(1858) published a review on lichen substances
already in 1858.
The classical period of lichen chemistry is
connected with two names: W. Zopf and O.
Hesse. W. Zopf (Fig. 1) was a botanist (born
1846 at Ro:Bleben, Thuringia, Germany, died
1909 at Miinster/Westfalen) and published
a series of papers on lichen substances which
he summarized in the well-known book Die
Flechtenstoffe in chemischer, botanischer,
pharmakologischer und technischer Beziehung,
published in 1907. Zopf's contrahent was the
chemist O. Hesse (born 1835 at Obereula, Fig. 1. W. Zopf
2 1 Introduction
Fig. 2. Y. Asahina Fig. 3. S. Shibata
lecanoric acid (Hesse 1900), which was synthe- Robinson and Schopf in the period between
sized by E. and H. Fischer in 1913. The structure 1920 and 1940.
of most lichen substances remained unknown A milestone in the field of lichen substances
till the beginning of the outstanding work of the was the publication of Chicita F. Culberson's
famous Japanese chemists Y. Asahina (born Chemical and Botanical Guide to Lichen Prod-
1880 in Tokyo, died 1975 in Tokyo; Fig. 2) and S. ucts, which appeared in 1969. Together with two
Shibata (born 1915 in Tokyo; Fig. 3) in 1921. supplementary volumes (C.F. Culberson 1970;
Asahina and Shibata published another clas- C.F. Culberson et al. 1977b), this trilogy summa-
sic, Chemistry of Lichen Substances, in 1954. rizes data of about 430 lichen substances and
Both scientists and their coworkers not only elu- their occurrence known up to 1976.
cidated the structure of numerous compounds, With the introduction of thin layer chroma-
but also described their synthesis and intro- tography in the 1960s and of high performance
duced the determination of lichen substances liqu,id chromatography later, the chemical
by microcrystallization, a remarkable progress analysis of lichens became routine, and modern
in times without thin layer chromatography spectroscopic methods (UV, IR, lH_ and 13C_
and high performance liquid chromatography. NMR, MS, ORD, CD, including X-ray analysis)
Other important work on the chemistry of li- allowed the structural elucidation of com-
chen substances was done by Koller, Pfau, pounds available in milligram amounts.
1.2 General Meaning of Lichen Substances and Their Use in Past and Present Time 3
During the past 30 years, many labora- chemistry and synthesis of depsides and
tories have been working on the chemistry xanthones but also an outstanding taxonomist,
of lichens, e.g. K. Aghoramurthy (India, especially of the family Parmeliaceae.
depsidones), B. Akermark (Sweden, aliphatic The field of chemistry and biochemistry of
acids, dibenzofuranes), F.W. Bachelor (Canada, lichen substances has been reviewed regularly
depsides), B. Bodo and 1. Molho (France, ali- since 1968 by Huneck (1968, 1971, 1984c, 1991),
phatic acids), T. Bruun (Norway, chromones, Elix et a1. (1984c), Galun (1988) and Fahselt
triterpenoids), J.D. Connolly (Great Britain, aro- (1994).
matic compounds), R.E. Corbett (New Zealand,
triterpenoids), C.F. Culberson and W.1. 1.2
Culberson (USA, depsides, TLC, chemotax- General Meaning of Lichen
onomy), B. Czeczuga (Poland, carotenoids), Substances and Their Use in Past
Dembitsky (Israel, lipids), H. Erdtman (Sweden, and Present Time
depsones and dibenzofuranes), A.G. Gonzalez
and J.B. Barrera (Spain, phenolic compounds),
1.2.1
S. Huneck (Germany, all groups of lichen sub-
Biological Activities of Lichen
stances, NMR, MS), K. Huovinen (Finland,
Substances
HPLC), M.F. Keogh (Venezuela, aliphatic com-
pounds, depsidones), J.P. Kutney (Canada,
The pharmacological activities of lichen sub-
usnic acid), C. Leuckert (Germany, xanthones,
stances to 1906 were summarized in Zopf's
chemotaxonomy, MS), B. Lindberg (Sweden,
monography (Zopf 1907). Subramanian (1966)
carbohydrates), W.S.G. Maass (Canada,
reported on drugs from lichens, while Hanssen
depsides), A. Mathey (France, quinones), O.B.
and Schadler (1985), Richardson (1988) and
Maximov and N.P. Mishchenko (Russia,
Schindler (1988) gave overviews on the medici-
depsidones, quinones), K. Moosbach (Sweden,
nal aspects of lichens.
biosynthesis), S. Neelakantan (India, dep-
According to more recent investigations, the
sidones), T.J. Nolan (Ireland, depsidones), G.
biological activities of lichens and lichen sub-
Quinkert (Germany, usnic acid, aspicilin), B.
stances can be divided into:
Renner (Germany, dibenzofuranes), J. Santesson
(Sweden, depsides, xanthones, t.1.c., MS), M.V. 1. Antibiotic Activity. Depsides (Ingolfsdottir
Sargent (Australia, depsidones, dibenzofuranes), et a1. 1985), depsidones and usnic acicl
T.R. Seshadri (India, depsides), Y.J. Solberg are active against Gram-positive micro-
(Norway, aliphatic compounds, steroids), W. organisms. The sodium salt of usnic acid
Steglich (Germany, quinones), G. Sundholm was used as a drug in Russia (Savicz
(Sweden, xanthones, NMR), R. Tabacchi (Swit- et al. 1960) and the water-soluble com-
zerland, synthesis of depsides and depsidones), pound of benzyldimethyl-(2-[2-p-(p-1,1,3,3-
K. Takahashi (Japan, usnic acid), Wachtmeister tetramethylbutylphenoxy)-ethoxy] ethyl)
(Sweden, dibenzofuranes), A.1. Wilkins (New ammonium hydroxyde was distributed as
Zealand, triterpenoids), Y. Yamamoto (Japan, USNO by the Laake Oy Pharmaceutical
culture oflichens), 1. Yoshimura (Japan, HPLC, Manufacturers in Finland (Laake Oy 1960); it
culture of lichens), 1. Yosioka (Japan, is active against impetigo, ecthyma, ulcus
triterpenoids). cruris, otitis, mastitis and moniliasis.
The worldwide leading lichen chemist is J.A. 2. Antitumour and Antimutagenic Activity.
Elix (Australian National Univiersity Canberra, The following lichen substances have
Australia), who is not only an expert in the antitumour and antimutagenic activity: (-)-
4 1 Introduction
usnic acid (Kupchan and Kopperman 1975; methylcryptochlorophaeic acid (prostaglan-

Takai et al. 1979), protolichesterinic and din synthetase) (Shibuya et al. 1983), extracts
nephrosteranic acids (Hirayama et al. from Vulpicida juniperinus (1.) J.-E.
1980), polyporic acid and derivatives (Cain Mattsson et M.-J. Lai, Hypogymnia physodes
1961, 1963, 1964, 1966), physodalic acid (1.) Nyl. and Letharia vulpina (1.) Hue (tyro-
(Shibamoto and Wei 1984), lichen glucans sinase) (Higuchi et al. 1992).
(Nishikawa et al. 1969, 1970, 1979; Hirayama 7. Other Activities. Picrolichenic acid was suc-
et al. 1980; Nishikawa and Ohno 1981; cessfully used against intermittent fever
Hirabayashi et al. 1989) and lichenin deriva- (Alms 1832; Zopf 1907). Pulvinic acid
tives (Demleitner et al. 1991). dilactone has a pronounced cardiotonic
3. Activity Against Human Immunodeficiency activity (Nador et al. 1954), secalonic acid
Virus (HIV). A sulfate (GE-3-S) prepared by A has a phlogistic activity (Harada et al.
chlorosulfonic acid treatment GE-3, a par- 1974) and vulpinic acid an antiinflamma-
tially acetylated ~(I --7 6)glucan from the li- tory activity (Foden et al. 1975). Usnic
chen Umbilicaria esculenta (Miyoshi) Mink., and diffractaic acids have analgesic and
inhibited the cytopathic effect of HI V in vitro antipyretic activities comparable to amino-
(Hirabayashi et al. 1989). phenazone, phenylbutazone and hydrocor-
4. Allergenic Activity. Numerous lichen sub- tisone hemisuccinate (Dobrescu et al. 1993;
stances like atranorin, barbatic, diffractaic, Okuyama et al. 1995).
evernic, fumarprotocetraric, lobaric, per-
latolic, physodic, physodalic, protoliches- 1.2.2
terinic, salazinic, stictic and usnic acids are Use of lichens in Folk Medicine
allergenes (Brasch and Jacobsen 1991).
5. Plant Growth Inhibitory Activity. Many li- Lichens have been used in folk medicine in
chen substances affect the growth of higher many countries. Well known is the application
plants (Follmann and Nakagava 1963; of Cetraria islandica (1.) Ach. against coughing
Ramaut and Thonar 1972a,b): and of Lobaria pulmonaria (1.) Hoffm. against
acetylportentol, atranorin, evernic acid, lung diseases (Schindler 1955). Nowadays, the
psoromic acid, virensic acid, (-)-usnic acid, medical use of lichens is rather obsolete, par-
(-)-iso-usnic acid, leprapinic acid, ticularly since the atom bomb tests in the atmo-
thiophanic acid (Huneck and Schreiber sphere and the Chernobyl accident in 1986
1972), vulpinic acid (Dauriac and Rondon increased the concentrations of dangerous
1976), roccellic acid (Garcia et al. 1982), radionucleides (e.g. 137Cs and 4K) by hundreds
stictic acid (Whiton and Lawrey 1982, 1984), and up to thousands of times the concentrations
lecanoric acid, barbatic acid, 4-0- of uncontaminated plants (Heinrich et al. 1989;
demethylbarbatic acid, 4-0-methylorsellinic Feige et al. 1990; Biazrov 1994).
acid, diffractaic acid, orsellinic acid As demonstrated in the preceding section, li-
(Nishitoba et al. 1987). chens synthesize a great variety of metabolites
6. Enzyme Inhibitory Activity. The with different structures and potential biologi-
following lichen substances were found to cal activities. It is no wonder that the large phar-
be enzyme inhibitors: lecanoric acid (histi- maceutical companies have initiated programs
dine decarboxylase) (Umezawa et al. 1974, for the application of these metabolites (and
1983), (-)-usnic acid (urease) (Vicente and their derivatives) in medicine and plant protec-
Cifuentes 1979; Garcia et al. 1980), 4-0- tion by a multitude of moderfi biotests. It can be
expected that the coming years will bring new 1.2.4

and interesting results in this field (Crittenden Lichens as Basic Material for Perfume
and Porter 1991).
Only two lichen species are used in large quanti-
1.2.3 ties as raw material for the perfume industry:
Lichens as Raw Material for Dyes Evernia prunastri (1.) Ach. and Pseudevernia
furfuracea (1.) Zopf. Up to 9000 tons of these
A short history of dyes from Roccella species two species have been processed annually
and other lichens was published by Kok (1966). (1986) at Grasse, the centre of the perfume in-
The invention of synthetic dyes in the mid-19th dustry in France (Moxham 1981). The ethanol
century brought the end of orchil manufacture. extract of both lichens has a typical "mossy"
Today, only small amounts of lichens are pro- flavour and is used not only as a component in
cessed for preparing litmus, the well-known pH certain perfumes ("Chypre"), but also as a
indicator (pH 4.5 red, pH 8.3 blue). Litmus is a fixative which keeps the flavour for a long time.
complex mixture of pigments, prepared mainly The essential compounds originate from the
from different Roccella species [e.g. R. phycopsis depsides present in the lichens by hydrolysis,
(Ach.) Ach., R. tinctoria DC.]. The lichens were decarboxylation of the corresponding hydro-
treated with ammonia (or urine) and air with xyacids and alcoholysis. Orcinol and methyl
addition of lime, potassium carbonate and gyp- everninate (sparassol) are compounds with the
sum. The litmus pigments are generated from typical mossy odour.
depsides like lecanoric acid and erythrin, which
yield orsellinic acid on hydrolysis. After decar- 1.2.5
boxylation, orsellinic acid gives orcinol, which The Biological Meaning
reacts in the presence of ammonia to orcein pig- of Lichen Substances
ments like a-aminoorcein, y-aminoorcein, and
~-oxyorcein (Zopf 1907; Musso 1960; Beecken et
Despite intensive research in the field of physi-
al. 1961).
ology and ecology, little is known about the
biological meaning of the many different me-
HO tabolites for the lichens themselves. Let us con-
sider the most important opinions:
1. Lichens usually are very slow-growing orgari-
isms and must be protected against lower
and higher plants: the lichen substances are
a-Aminoorcein active protective and antibiotic substances
(Hess 1960; Whiton and Lawrey 1982, 1984;
Ingolfsdottir et al. 1985).
HO OH
2. Aromatic lichen substances absorb UV light
and protect the algae against too intensive
irr<j.diation (RundeI1978; Lawrey 1986).
3. Lichen substances affect the permeability of
the cell walls of the phycobionts, and could
y-Aminoorcein: R = NH2 play an important role in symbiotic equilib-
~-Oxyorcein: R = OH rium (Follmann and Villagran 1965; Kinrade
6 1 Introduction
and Ahmadjian 1970; Schimmer and Lehner Herzig et al. 1987; Galun and Ronen 1988;
1973). John 1988, 1989; Herzig 1990). The exten-
4. Certain aliphatic and aromatic lichen acids sive literature concerning air pollution and
(e.g. norstictic, iso-usnic and usnic acids) lichens is summarized continuously in the
are strong chelating agents and are essential Lichenologist.
for supplying the lichen with minerals from
the substrate (Schatz 1962; Follmann and 1.2.7
Peters 1966; Syers and Iskandar 1973; Lichens and Biodeterioration
Engstrom et al. 1980; Purvis et al. 1987; Jones
1988).
A very modern ecological aspect of lichens is
5. Lichen substances act as antifeedants for in-
biodeterioration, which means the deterioration
sects and other animals (Lawrey 1983, 1986;
and destruction of ancient frescoes, coloured
Ahad et al. 1991; Emmerich et al. 1993; Giez
windows of cathedrals and old buildings by
et al. 1994).
incrustation with lichens. The lichen Dirina
6. Many lichens grow under extreme conditions
massiliensis Durien et Mont. has already de-
concerning change of temperature, humid-
stroyed the painted frescoes of the Palazzo
ity, and intensity oflight. Recent research has
Farnese in Caprarola, Italy. Similar damages
shown that plants under stress conditions are
have been noted on Greek sculptures and on
able to synthesize so-called stress metabo-
the Arch of Trajan. Fourier transform micros-
lites, and it is likely that lichens respond to
copy has shown that the lichens produce oxalic
such extreme changes in their environment
acid, which converts the calcium carbonate
by the synthesis of large amounts of stress
of the substrate to calcium oxalate, changing
metabolites. The crustose species Pertusaria
the structure of the surface (Edwards et al.
alaianta Nyl. from the Cape Verde Islands
1993).
with hot and arid climate contains up to 20%
dry weight of a mixture of chloroxanthones
(Huneck and Hafle 1978). Such high 1.2.8
amounts of secondary compounds can Chemotaxonomy of Lichens
hardly be found in higher plants. Lange
(1992) has discussed this topic in detail. Chemistry plays an important role in the
7. Lichen substances excreted in the medulla taxonomy of lichens, as a modern monograph
have hydrophobic properties to prevent the of a lichen taxon demonstrates. [See, for ex-
saturation of the medulla with water and ample, Lumbsch (1994), Lumbsch et al. (1994),
to allow continuous gas exchange with the and Knoph et al. (1995)]. One reason is that
atmosphere (Armaleo L993). lichens are difficult to differentiate morphologi-
cally, but can well be distinguished by their sec-
1.2.6 ondary metabolites, which are often present
Lichens as Biomonitors in considerable quantities. Hale (1966), W.L.
Culberson (1969), W.L. Culberson and C.F.
Most lichens are very sensitive to sulphur diox- Culberson (1970), Hawksworth (1976) and
ide and other industrial effluents; hence they are Brodo (1978) have summarized the application
useful indicators for monitoring air pollution of chemical criteria in lichen taxonomy. Feige
(Doll and Ziebold 1976; Nash III 1976; and Lumbsch (1995) have discussed the differ-
Richardson and Nieboer 1981; Haseloff 1982; ent kinds of chemical variation in lichens.
A simple but striking example is the occur- Three patterns of chemical variation can be
rence of both antipodes of usnic acid in different distinguished:
lichen genera:
1. replacement type compounds,
2. chemosyndromic variation, and
Lichen genus Usnic acid 3. accessory type compounds.
Alectoria (-) Congeneric chemotypes show simple re-
Cetraria (-) placement of one compound. Pseudevernia
Cladina (+)
Cladonia (-)
furfuracea (1.) Zopf occurs in Europe in two
Evernia (+) races containing olivetoric or physodic acids,
Haematomma (-) while the race from North America synthesizes
Lecanora (+) lecanoric acid.
Lobaria (+) In a chemosyndrome, one main compound is
Nephroma (+)
accompanied by minor substances which are
Ophioparma (+)
Parmelia (+) biosynthetically closely related. Four species of
Ramalina (+) the Lecanora subfusca group (Lumbsch 1994)
Rhizoplaca (-) (L. elixii Lumbsch, L. epibryon Ach., L.
Rinodina (+) mayrhoferi Lumbsch, and L. parmelinoides
Squamarina (-)
Lumbsch) belong to a chemosyndrome with
Usnea (+)
2,5,7 -trichloro-3-0-methylnorlichexanthone as
Table 1. Lichen substances from complete lichens, their mycobionts and lichen culture
Lichen Lichen substances from:
Intact lichen Mycobiont Lichen culture Literature
Anaptychia hypoleuca Atranorin + Ejiri and Shibata (1974)

Chloroatranorin +
Norstictic acid +
Salazinic acid +
Zeorin Zeorin +
Baeomyces rufus Constictic acid Ergosterol Renner and Gerstner (1982)
Cryptostictic acid Triglyceride
Norstictic acid
Stictic acid
Caloplaca ferruginea 7-Chloroemodin 7-Chloroemodin Renner and Gerstner (1978a)
Emodic ~cid
Emodin
Fallacinal
Parietin
Cladonia crispata Squamatic acid Squamatic acid Ejiri and Shibata (1975)
Cladonia graciliformis Bellidiflorin Bellidiflorin Ejiri et al. (1975)
Rhodocladonic acid
Squamatic acid
Usnic acid
Lecanora dispersa 2,7-Dichloroliche- Pannarin Leuckert et al. (1990a)
xanthone Dechloropannarin
8 1 Introduction
Table 1. Continued
Lichen Lichen substances from:
Intact lichen Mycobiont Lichen culture Literature
Lecanora rupicola Atranorin Eugenitin Fox and Huneck (1969)

Chloroatranorin Eugenitol
Roccellic acid Roccellic acid
Sordidone Sordidone
Thiophanic acid
Ramalina crassa Salazinic acid Salazinic acid Kurokawa (1971)
Sterol Sterol
Usnic acid Usnic acid
Ramalina siliquosa Atranorin 4-0- Demethylbarbatic Hamada and Ueno (1987)
acid Hamada (1989)
Protocetraric acid
Salazinic acid
(+)-Usnic acid
Ramalina yasudae Evernic acid Protocetraric Yamamoto (1985)
acid
Salazinic acid
Usnic acid
Stereocaulon Atranorin Lecanoric acid Hamada and Ueno (1990)
curtatum Lecanoric acid
Miriquidic acid
Usnea diffracta Usnic acid Usnic acid Yamamoto (1990)
Usnea flexilis Usnic acid Protocetraric Protocetraric Yoshimura et al. (1989)
acid acid
Salazinic acid Salazinic acid
Usnea longissima Usnic acid Usnic acid Yamamoto (1990)
Usnea rubescens Evernic acid Usnic acid Yamamoto (1985)
Salazinic acid
Usnic acid
Xanthoria mand- Erythroglaucin Erythroglaucin Nakano et al. (1972)
schurica Erythroglaucinic Erythroglaucinic
acid acid
Parietin Parietin
Xanthoria fallax Atranorin Emodin Nakano et al. (1972)
Fallacinal Erythroglaucin
Parietin Erythroglaucin
Telo'schistin carboxylic acid
Fallacinal
Fallacinol
Parietin
major component (Lumbsch et al. 1994). The characterized by the occurrence of numerous
distribution and chemistry of the saxicolous chloroxanthones.
species of Lecidella has been reviewed by Accessory metabolites are substances which
Knoph et al. (1995). This genus is also occur sporadically in a species; they have little
1.3 Culture of Lichens and Their Symbionts 9
or no taxonomic significance (Elix et al. 1993), while the culture of the phycobionts
1984c). starts with an isolated cell (Ahmadjian 1967,
1993). Cultures oflichen tissues containing both
1.3 symbionts are also possible. The typical lichen
Culture of Lichens metabolites are built by the mycobiont only, but
and Their Symbionts there are great qualitative and quantitative dif-
ferences in the spectrum of these metabolites
Lichens and their mycobionts have long been between the complete lichen, the cultured fun-
considered as being extremely difficult to culti- gus and the lichen culture, as demonstrated in
vate. Recently, however, great progress has been Table l.
made in this field. The lichen fungi can be culti- Research in the field of cultivating lichens
vated either from spores or from fungal cell ag- and their symbionts opens a door to the mass
gregates (Yamamoto 1990; c.P. Culberson and production of lichen substances and their phar-
Armaleo 1992; Kinoshita 1993; Yamamoto et al. maceutical and technical application.
2 Identification of Lichen Substances
The number of lichen substances with known 50C, pressure 350bar, time 6h, flow rate 20kg
structure is about 700. It is the aim of this book CO 2 per h for the extraction of usnic acid from
to help the lichenologist and the natural product Usnea barbata. For micro scale extraction, ac-
chemist in the identification of this large group etone is recommended, as most lichen sub-
of plant metabolites. It comprises methods for stances are soluble in this solvent. The use of the
the isolation and identification of lichen sub- micro extractor shown in the monograph of
stances by physical and spectroscopic methods, Asahina and Shibata (1954) cannot be recom-
micro crystallization, thin layer chromatogra- mended because of the risk of inflammation of
phy, high performance liquid chromatography, the solvent. A simple and safe device is shown in
gas liquid chromatography and derivatization. Fig. 4.
The main part contains the formulae, molecular The finely ground lichen (0.1-1g) is boiled
weights and data about the melting points, three times with a few ml of acetone in a test tube
colour reactions, UV, IR, lH-NMR, 13C-NMR (6 x 160mm) for some minutes, the hot solution
and mass spectra, derivatives, TLC RF-values, filtered through a soft filter and the combined
microcrystallization, HPLC and the standard li- extracts are concentrated to a volume of 2-3 ml.
chen (which contains the corresponding com- For amounts in the range of 5-100 g oflichen
pound) with references of all lichen substances material, a modified Soxhlet apparatus (Fig. 5)
described in the literature up to 1995. Tables of has proved very efficient.
molecular weights, melting points and reactions Extraction has to be continued until all lichen
of lichen substances are further auxiliaries. Fi- substances are dissolved (6-60h). Often heavily
nally, a key for the identification of lichen soluble compounds precipitate in the extract
substances is presented. and can be removed by filtration. One way to
A useful guide to microchemical techniques work up the extract is separation in an acid, a
for the identification of lichen substances was phenolic and a neutral part, by shaking succes-
published by White and James (1985). sively with a solution of NaHC0 3 (10% in H20)
and NaOH (2% in H 20). Some compounds, e.g.
2.1 chlorinated phenolics, are soluble in a solution
Extraction and Purification ofNa2C0 3 (5% in H2 0). Shaking should be con-
of Lichen Substances tinued for 10-15min. Another way is chroma-
tography of the extract over silica gel. The ratio
Because of the different solubility of the lichen of prod~ct to adsorbent is about 1: 30 to 1: 50,
substances in different solvents, fractionate ex- and an approved sequence of eluents is n-hex-
traction can be used. An approved sequence is n- ane-diethyl ether-methanol. Many extracts are
hexane-diethyl ether-acetone-methanol. Ribar heavily soluble in n-hexane; to overcome this
et al. (1993) used supercritical CO 2 (temperature difficulty, the mixture is dissolved in a proper
12 2 Identification of Lichen Substances
air gap
inlet - - _____,
outlet _
of cooling water
- - - - test tube
- - solvent
- - - - electric water bath

extraction - - ------
Fig. 4. Microscale extraction of a lichen filter
solvent, e.g. acetone or chloroform, silica gel

added (in the ratio 1: I), the solvent removed
i.vac., the adsorbent with the mixture placed on
the top of a column with silica gel and elution
started with n-hexane.
250 - 500 ml round bottomed flas
An effective method for the separation and / solvent with boiling
purification oflichen substances is the prepara- stones
tive thin layer chromatography. After having
chosen a suitable solvent, the mixture is applied
electric water bath
to a 10 x 10 cm plate with a layer of 1 mm silica
gel Merck PF 254 + 366 as a straight line. Ten to Fig. 5. Modified Soxhlet apparatus for the extraction of
20 mg can be separated by a plate of this size. large amounts of lichens
After running the chromatogram, the solvent is
evaporated at room temperature under a hood Sometimes it is possible to separate a mixture
and the bands containing the compounds are oflichen substances by their different solubility.
made visible under a UV lamp, by treatment Usnic acid and atranorin are very soluble in
with iodine vapour or by spraying a small stripe chloroform, but nearly insoluble in methanol.
of the plate with a suitable reagent. The bands Suitable solvents for recrystallization are n-
are marked with a needle, removed from the hexane, benzene, diethyl ether, acetone, ethyl
plate and extracted with diethyl ether or acetone acetate, methanol, ethanol, acetic acid, dioxane
for 5-10min. The silica gel is removed by or water; often mixtures of these solvents are
filtration, the solvent evaporated i.vac. and the used. Sugar and low molecular carbohydrates
residue recrystallized. The rate of recovery is are well known for their poor tendency to crys-
about 50-60%. tallize. Very important is the use of diethyl ether
Less to medium polar compounds can be rap- and dioxane free from peroxides, which are
idly separated by flash chromatography (Still et highly explosive. A simple reaction to test these
al. 1978). solvents for peroxides is to shake about 3 ml of
2.3 Colour Reactions and Other Reactions for the Identification of Lichen Substances 13
the solvent with a solution of potassium iodide groups or elements in the molecule of a lichen
in diluted acetic acid (0.05g KJ in 2ml HzO with substance.
two drops of AcOH). In the presence of per- Acids turn the colour of litmus paper from
oxides the colourless solution turns yellow blue to red.
or brown. Potassium hydroxide (20% KOH in 100mi
HzO) is a useful reagent to differentiate between
2.2 quinones and compounds of the pulvinic acid
Melting Point group: the orange or red colour of the quinones
turns to deep red. Atranorin and related com-
The melting point is an important criterion for pounds give a deep yellow colour with KOH.
the identification of a pure lichen substance and Norstictic acid forms a deep red microcrystal-
can be measured with a few crystals either in a line complex with KOH.
glass capillary or under the microscope with a Sodium hypochlorite (NaOel, in the
Kofler apparatus. Some compounds (e.g. lichenologicalliterature abbreviated as Cl or C)
physodalic and salazinic acids) do not have a [prepared by reaction of chlorine (7 g) with
sharp melting point, but decompose over a wide NaOH (8g) in distilled water (lOOml) at OC;
range. Other substances (e.g. tenuiorin) have a this solution decomposes in time and should be
double melting point: they melt at a certain tem- stored in a refrigerator] is a reagent for depsides
perature, recrystallize and melt once again at a and xanthones containing two free hydroxyl
higher temperature. Certain lichen substances groups in meta-position. The colour turns from
tent to crystallize with solvent, which can be colourless or yellowish to red, but is often rather
removed by heating under vacuum. Many aro- instable and fades away in a few seconds. For
matic carboxylic acids melt under decarboxyla- this reason, the reagent should be added
tion. Identification of a substance with a known dropwise. In some cases (e.g. olivetoric acid),
and available compound is easily done by a the colour develops only after preliminary addi-
mixed melting point: a few crystals (about 1 mg) tion ofKOH (abbreviated as K + Cl or K + C), as
of both compounds are mixed thoroughly and the depside ester group has to be hydrolyzed.
the melting point of the mixture is determined. Some dibenzofuranes, like didymic, pannaric,
If both compounds are identical, the mixture porphyrilic acids and strepsilin, show a very
melts without depression. characteristic green coloration with NaOCI.
On heating the glass capillary in a flame, the Table 2 summarizes the lichen substances
lichen substances decompose and evolve char- which give a colour reaction (red, orange or'
acteristic odours. It is easy to differentiate be- green) with sodium hypochlorite.
tween an aliphatic compound, a phenolic or a A solution of barium hydroxyde [Ba(OH)2] in
triterpene in this way. water gives a blue colour with diploschistesic
acid, and a saturated solution of barium perox-
2.3 ide (BaO z) in water with olivetoric acid gives a
Colour Reactions and Other lemon yellow colour, turning to green after
Reactions for the Identification some minutes.
An ethanolic solution of p-phenylenediamine
of Lichen Substances
(2-5%) gives yellow to orange colours with
depsides and depsidones containing an alde-
Some colour and other reactions give useful
hyde group; the reaction products are Schiff
hints for the presence of certain functional
bases:
Table 2. Lichen substances which give a colour reaction (red, orange or green) with sodium hypochlorite
Alectorialic acid 2,5-Dichloronorlichexanthone 2'-0-Methylnorsuperphyllinic acid

Alectorialin 2,7 -Dichloronorlichexanthone Methyl ~-orcinolcarboxylate
~-Alectoronic acid 4,5-Dichloronorlichexanthone Methyl orsellinate
Anziaic acid 4,7 -Dichloronorlichexanthone 9-Methyl pannarate
Arthoniaic acid 5,7 -Dichloronorlichexanthone 2' -0-Methylphenarctin
Arthothelin Diploschistesic acid 2' -0-Methylpseudocyphellarin A
Asemone Divaricatic acid 6-0-Methylthiophanic acid
Barbatolic acid Divarinol Montagnetol
Barbatolin Erythrin Nephroarctin
Bis-(2,4-dihydroxy-6-n-propyl)- Ethyl orsellinate Nordivaricatic acid
methane Eugenitol Nor-iso-obtusatic acid
5-Chloro-4-0-demethylbarbatic acid Gyrophoric acid Norlichexanthone
2-Chloro-6-0-methylnorlichexanthone Hiascic acid Norlobariol
4-Chloro-6-0-methylnorlichexanthone Hyponephroarctin Normiriquidic acid
5-Chloro-6-0-methylnorlichexanthone Isolecanoric acid Olivetol
7-Chloro-6-0-methylnorlichexanthone Isonorobtusatic acid Olivetolcarboxylic acid
2-Chloronorlichexanthone Isopseudocyphellarin A Olivetoric acid
4-Chloronorlichexanthone Lecanoric acid Orcinol
5-Chloronorlichexanthone Loxodinol ~-Orcinol
7-Chloronorlichexanthone 2'-0-Methylanziaic acid Orcinyllecanorate
~-Collatolic acid 6-0-Methylarthothelin ~-Orcinolcarboxylic acid
Congrayanic acid 6-0-Methylasemone Orsellinic acid
Crustinic acid Methyl 5-chloro-4-0- Ovoic acid
Cryptochlorophaeic acid demethylbarbatate Pannaric acid
4-0-Demethylbarbatic acid Methyl 5-chloronorobtusate Phenarctin
4-0-Demethylglomellic acid Methyl 4-0-demethylbarbatate Porphyrilic acid
4-0-Demethylglomelliferic acid Methyl 3,5-dichlorolecanorate Protosiphulin
4-0-Demethylloxodellic acid Methyleriodermate Pseudocyphellarin A
4-0-Demethylmicrophyllinic acid Methyl gyrophorate Pseudocyphellarin B
4-0-Demethylsphaerophorin 2"-0-Methylgyrophoric acid meta-Scrobiculin
4-0-Demethylsquamatic acid 5-0-Methylhiascic acid Siphulin
4-0-Demethylstenosporic acid 2' -O-Methylhiascic acid Sordidone
4-0-Demethylsuperconfluentic acid Methyl 8-hydroxy-4-0- Strepsilin
3,5-Dichloro-2'-0-methylanziaic acid demethylbarbatate Submerochlorophaeic acid
2,5-Dichloro-6-0- 2'-0-Methyl-iso-pseudocyphellarin A Subpaludosic acid
methylnorlichexanthone Methyllecanorate Thiophanic acid
2,7 -Dichloro-6-0- Methyl 2'-0-methyleriodermate Thiophaninic acid
methylnorlichexanthone Methyl 3'-methyllecanorate 2,4,7 -Trichloro-6-0-
4,5-Dichloro-6-0- 2' -0-Methylnorbarbatic acid methylnorlichexanthone
methylnorlichexanthone 4'-0-Methylnorcryptochlorophaeic 2,5,7 -Trichloro-6-0-
4,7-Dichloro-6-0- acid methylnorlichexanthone
methylnorlichexanthone 4' -0-Methylnorhomosekikaic acid 2,4,5-Trichloronorlichexanthone
5,7-Dichloro-6-0- 6-0-Methylnorlichexanthone 2,4,7 -Trichloronorlichexanthone
methylnorlichexanthone 2' -0-Methylnorobtusatic acid 2,5,7-Trichloronorlichexanthone
2,4-Dichloronorlichexan thone 4'-0-Methylnorsekikaic acid
2.4 UV Spectroscopy 15
R-CHO + P-H2N-C6 H4-NH2 ~ A similar diagnostic colour reagent,

R-CH=N-C 6H4-NH2 + H20. Dimroth's reagent, is a solution of boric acid
(B(OH)3' 2%) in acetic anhydride. Quinones
The solution must be freshly prepared; it be- with a ~-hydroxyl group give red to violet
comes dark brown in the presence of air in the colours (boroacetate complexes).
course of 30min. p-Phenylenediamine should The Beilstein test is a simple but sensitive
be handled with great care and never brought and reliable test for lichen substances contain-
into contact with the skin or even inhaled being chlorine. The compound (1 mg) is
cause it is cancerogenic. brought on the tip of a freshly glowed copper
Table 3 shows the monocyclic aromatic com- wire into the flame of a Bunsen burner: a deep
pounds, depsides, and depsidones which give a green flame develops for a moment in the
colour reaction (yellow, orange or red) with p- presence of chlorine (or another halogen) in the
phenylenediamine. substance.
An ethanolic solution of iron-III-chloride Table 4 summarizes the chlorine-containing
(FeCI3, 1%) is a test for phenolic groups (brown, lichen substances which give a positive Beilstein
red, wine red or violet coloration); in some cases test.
the colour changes after addition of some drops
of water. 2.4
An ethanolic solution of magnesium acetate UV Spectroscopy
[Mg(OAcL, 2%] gives red to violet colorations
with quinones having a free hydroxyl group in The molecular extinction coefficient is calcu-
the ~-position. lated by the formula
Table 3. Monocyclic aromatic compounds, depsides and depsidones which give a colour reaction (yellow, orange or red)
with p-phenylenediamine
a-Acetylconstictic acid 2'-0-Demethylpsoromic acid Norargopsin

a-Acetylsalazinic acid 8' ,9'-Di-O-ethylsalazinic acid Nordeehloropannarin
Alectorialic acid Eriodermin Norpannarin
Alectorialin Ethyl haematommate Norstictic acid
Allorhizin Fumarprotocetraric acid Pannarin
Argopsin Furfuric acid Phenaretin
Atranol Haemathamnolic acid Phyllopsorin
Atranorin Haematommic acid Ph ysciosporin
Baeomycesic acid Hyponephroarctin Physodalic acid
Barbatolic acid Isopseudocyphellarin A Protocetrarie acid
Barbatolin Malonprotoeetrarie acid Pseudocyphellarin A
Chloroatranol 2'-0-Methylatranorin Psoromic acid
Chloroatranorin Methyl 5,1'-dichloronorpsoromate Salazinic acid
Chlorogranulatin Methyl 5, l'-dichloropsoromate Siphulellic acid
l' -Chloronephroarctin 2'-0-Methyl-iso-pseudoeyphellarin A Stietic acid
Chlorophyllopsorin 2' -O-Methylphenarctin Substictic acid
Constictic acid 2' -O-Methylpseudocyphellarin A Suecinprotoeetraric acid
Cyclographin Methylstictic acid Thamnolic acid
Decarboxythamnolic acid Methyl virensate Vesuvianic acid
Dechloropannarin Nephroarctin Virensic acid
4-0-Demethylbaeomycesic acid
Table 4. Chlorine-containing lichen substances which give a positive Beilstein test
Allorhizin methylnorlichexanthone Methyl 5-chloronorobtusate

Argopsin 2,5-Dichloro-3-0- Methyl 3,5-dichlorolecanorate
Asemone methylnorlichexanthone Methyl 5,1'-dichloronorpsoromate
Arthothelin 2,5-Dichloro-6-0- MethyI5,1'-dichloropsoromate
Buellolide methylnorlichexanthone MethyI2,2'-di-0-methyleriodermate
Caloploicin 2,7 -Dichloro-3-0- 4-0-Methyldiploicin
Canesolide methylnorlichexanthone Methyl eriodermate
Chloroatranol 2,7 -Dichloro-6-0- MethyI2-0-methyleriodermate
Chloroatranorin methylnorlichexanthone MethyI4-0-methyleriodermate
5-Chloro-4-0-demethylbarbatic acid 4,5-Dichloro-3-0- Methyl 2' -O-methyleriodermate
3-Chlorodivaricatic acid methylnorlichexanthone 4-0-Methylphysciosporin
5-Chlorodivaricatic acid 4,5-Dichloro-6-0- 8-0-Methylthiomelin
7-Chloroemodin methylnorlichexanthone 3-0-Methylthiophanic acid
Chlorogranulatin 4,7 -Dichloro-3-0- 6-0-Methylthiophanic acid
3-Chloroimbricaric acid methylnorlichexanthone 4-0-Methylvicanicin
Chlorolecideoidin 4,7-Dichloro-6-0- Norargopsin
2-Chlorolichexanthone methylnorlichexanthone Norgangaleoidin
4-Chlorolichexanthone 5,7 -Dichloro-3-0- Norpannarin
5-Chlorolichexanthone methylnorlichexanthone Northiomelin
7-Chlorolichexanthone 5,7 -Dichloro-6-0- Norvicanicin
7-Chloro-1-0-methylemodin methylnorlichexanthone Nostoclide I
2-Chloro-3-0-methylnorlichexanthone 2,4-Dichloronorlichexan thone Nostoclide II
2-Chloro-6-0-methylnorlichexanthone 2,5-Dichloronorlichexanthone Pannarin
4-Chloro-3-0-methylnorlichexanthone 2,7-Dichloronorlichexanthone Papulosin
4-Chloro-6-0-methylnorlichexanthone 4,5-Dichloronorlichexanthone Phyllopsorin
5-Chloro-6-0-methylnorlichexanthone 4,7-Dichloronorlichexanthone Physciosporin
7-Chloro-3-0-methylnorlichexanthone 5,7 -Dichloronorlichexanthone Scensidin
7-Chloro-6-0- 1,7-Dihydroxy -4,5-dichloro-6,8- Sordidone
methylnorlichexanthone dimethoxyxanthone 1,2',7,7'-Tetrachlorohypericin
5-Chloronephroarctin 1,5-Dimethoxy-4-chloro-6-methyl-8- Thiomelin
2-Chloronorlichexanthone hydroxyxanthone Thiophanic acid
4-Chloronorlichexanthone 2,7-Dimethoxy-3-methyl-5-hydroxy- Thiophaninic acid
5-Chloronorlichexanthone 6-chloroanthraquinone Thuringione
7-Chloronorlichexanthone Diploicin 2,4,5-Trichloro-3,6-di-0-
3-Chloroperlatolic acid Eriodermin acetylnorlichexanthone
Chlorophyllopsorin Flavoobscurin A 2,4,5-Trichlorolichexanthone
3-Chlorostenosporic acid Flavoobscurin B j 2,4,7 -Trichlorolichexanthone
Chlorovinetorin Flavoobscurin B, 2,5,7-Trichlorolichexanthone
Cyclographin Fragilin 4,5,7 -Trichlorolichexanthone
3-Dechlorodiploicin Fulgidin 2,4,7-Trichloro-3-0-
3-Dechlorogangaleoidin Fulgoicin methylnorlichexanthone
3' -Dechlorolecideoidin Gangaleoidin 2,4,7 -Trichloro-6-0-
3-Dechloro-0-methyldiploicin 1-Hydroxy-2,4-dichloro-6,8- methylnorlichexanthone
2-Dechloro-8-0-methylthiomelin dimethyl-7-methoxyxanthone 2,5,7-Trichloro-3-0-
4-Dechloro-8-0-methylthiomeiin Hypophysciosporin methylnorlichexanthone
2-Dechlorothiomelin Isofulgidin 2,5,7-Trichloro-6-0-
4-Dechlorothiomelin Isovicanicin methylnorlichexanthone
Demethylchodatin Lecideoidin 2,4,5-Trichloronorlichexanthone
3-0-Demethylscensidin Leoidin 2,4,7 -Trichloronorlichexanthone
7,7'-Dichlorohypericin 1-Methoxy-4-chloro-5,8-dihydroxy-6- 2,5,7-Trichloronorlichexanthone
5,7 -Dichloroemodin methylxanthone 1,6,8-Trihydroxy-3-methyl-7-
2,4-Dichlorolichexanthone 6-0-Methylarthothelin chloro-10-anthrone
2,5-Dichlorolichexan thone 3-0-Methylasemone 1,5,8-Trimethoxy-2-chloro-6-
2,7 -Dichlorolichexanthone 6-0-Methylasemone methylxanthone
4,5-Dichlorolichexanthone 1-0-Methyl-7 -chlorocitreorosein Tri-O-methylarthothelin
4,7 -Dichlorolichexanthone 1-0-Methyl-7 -chloroemodin Vicanicin
5,7 -Dichlorolichexanthone Methyl 5-chloro-4-0- Vinetorin
3,5-Dichloro-2'-O-methylanziaic acid demethylbarbatate Wrightiin
2,4-Dichloro-3-0-
2.4 UV Spectroscopy 17
d (logE 3.75). Depsidones with an aldehyde group

E=-, at position 3 show maxima in the range of211-
cl
216 (logE 4.46), 234-242 (logE 4.42), and 310-
with d = optical density, c = concentration of the 321 nm (logE 3.68). Table 6 contains the UV
solution in mol/liter and 1 = length of the cell in data of nine selected depsidones.
cm. Either E or logE is given in the literature.
Pure methanol or ethanol are the common sol- 2.4.3
vents for the UV spectroscopy of lichen y-Lactones
substances.
a-Methylene-y-lactones can be easily distin-
2.4.1 guished from the corresponding isomer a,~
Oepsides unsaturated y-lactones by their UV spectra, as
demonstrated in Table 7.
The UV maxima of depsides of the orcinol type
range between 207 and 225, 254 and 275, and 282 2.4.4
and 318nm with log E 4.60,4.23 and 4.00 respec- Chromones and Xanthones
tively. Table 5 contains the UV maxima and
logE values of 15 selected depsides. Chromones are characterized by five UV
maxima in the range of 228-234 (logE 4.34),
2.4.2 242-253 (logE 4.31), 251-263 (logE 4.31), 278-
Oepsidones 296 (logE 3.99) and 313-335nm (logE 3.62) and
xanthones by four UV maxima in the range of
Depsidones of the orcinol type are characterized 240-256nm (logE 4.53), 266-279 (logE 4.10),
by UV maxima in the range of 208-224 (logE 308-322 (logE 4.21) and 340-370nm (logE
4.46), 250-270 (logE 4.13), and 300-333nm 4.03). The maxima of chromones and xanthones
Table 5. UV data of 15 selected depsides
Depside Amax. nm (loge)
Atranorin 210 (4.20) 252 (4.16) 312 (3.57)

Chloroatranorin 213 (4.21) 252 (3.99) 282 (3.94)
Alectorialic acid 219 (4.45) 243 (4.49) 263 (4.47) 335 (3.75)
Baeomycesic acid 212 (4.41) 247 (4.08) 288 (3.84)
Haemathamnolic acid 222 (4.50) 283 (4.39)
Nephroarctin 238 (3.81) 281 (4.09) 315 (4.00)
Phenarctin 254 (4.49) 283 (4.46) 313 (4.47)
Pseudocyphellarin A 218 (4.15) 250 (4.36) S 270 (4.21) 342 (3.30)
S 290 (3.96)
Arthoniaic acid 270 (4.28) 300 (4.15)
Confluentic acid 268 (4.18) 304 (3.86)
Glomellic acid 258 (4.19) 308 (3.97)
Glomelliferic acid 268 (4.17) 306 (4.11)
2-0-Methylconfluentic acid 260 (3.86) 284 (3.75)
4-0-Methylconfluentic acid 269 (4.15) 308 (3.99)
Olivetoric acid 270 (4.16) 305 (4.11)
Table 6. UV data of nine selected depsidones
Depsidone A.max' nm (logE)
Colensoic acid 256 (4.2) 310 (3.3)

Diploicin 215 (4.3) 322 (3.97)
Gangaleoidin 208 (4.32) 320 (3.68)
Grayanic acid 258 (4.10) 300-310 (3.5)
o:-Alectoronic acid 211 (4.49) 260 (3.94) 310 (3.54)
o:-Col1atolic acid 213 (4.58) 255 (4.08) 313 (3.56)
Lobaric acid 212 (4.54) 260 (3.96) 295 (3.78)
4-0-Methylphysodic acid 211 (4.67) 260 (4.15)
Physodic acid 212 (4.65) 263 (4.06) 314 (3.49)
Table 7. UV data of o:-methylene-y-lactones and o:,~

unsaturated y-lactones
y-Lactone
2.4.7
Protolichesterinic acid 218 (3.82) Quinones
Murolic acid 216 (3.74)
Lichesterinic acid 227 (4.17)
Neuropogonic acid 227 (4.10)
The UV data of 11 quinones from lichens are
summarized in Table 8.
with a hydroxyl group in p-position to the car- 2.5

bonyl group are shifted to higher values on ad- IR Spectroscopy
dition of small amounts of AlCl 3, as shown for
7-chloronorlichexanthone: UV, A~~H (nm): 243, IR spectroscopy is a reliable method for the
270,345; UV, A~~~H+AIC13 265, 342, 392nm. identification of lichen substances. Solid com-
pounds can be measured either in solution (CCl4
2.4.5 or CHCl3 ), suspension (Nujol) or preferably in
Dibenzofuranes KBr. The IR spectra of liquids are recorded as a
film between two NaCl windows.
Dibenzofuranes show UV maxima in the range Intermolecular hydrogen bonds appear in the
of236-249 (logE 4.53),256-274 (loge 4.30), and region of 3200-3500 cm-1 and disappear on dilu-
310-330nm (logE 3.90). The data of usnic acid tion (recorded in CCl4 or CHCl3 ), while bands of
and related compounds are 220-232 (logE 4.23), intramolecular bonds in the range of 3450-
282-290 (logE 4.41), and 325-340nm (logE 3570 cm- 1 do not change on dilution.
3.63). The carbonyl band of five-membered lac-
tones (y-lactones) is in the range of 1735-
2.4.6 1750cm-1, while six-membered lactones
Pulvinic Acid Derivatives (8-lactones) absorb in the range of 1760-
1780cm-1 Five-membered anhydrides show
Maxima in the range of 253-291 and 316- two CO bands at 1770 and 1844cm-1, but six-
383 nm seem to be characteristic of pulvinic acid membered anhydrides absorb at 1758 and
derivatives. 1790cm- 1
2.6 NMR Spectroscopy 19
Table 8. UV data of 11 lichen quinones
Quinone Amax' nm (logE)
Averantin 223 (4.53), S 258 (4.18),266 (4.24), S 287 (4.47),294 (4.53), 325 (4.01),454 (4.03)
Canarione S 214 (3.85), 242 (4.02),270 (3.87), 380 (3.25), 500 (3.09)
7-Chloroemodin 220 (4.45), 255 (4.16),273 (4.32),282 (4.33), S 308 (4.07), 437 (4.01), 458 (3.96), S 515 (3.17)
Citreorosein 221 (4.41),252 (4.19), S 266 (4.16), 290 (4.19),438 (3.95), S 458 (3.94)
Emodin 253 (4.31),266 (4.29),289 (4.36),436 (4.14)
Fallacinal 224 (4.49),250 (4.21),265 (4.23),287 (4,21),433 (4.06), S 455 (4.03)
Haematommone 205 (4.67),235 (4.71),269 (4.43),310 (4.63), 464 (4,18)
Parietin S 257 (4.35), 266 (4.36), 288 (4.35),431 (4.20)
Rhodocladonic acid 294 (4.37), S 318 (4.18), S 328 (3,99),449 (3.65)
Skyrin 218 (4.85), 259 (4.76),298 (4.51),462 (4.38)
Trypethelone 274 (4.54), 283 (4.55),316 (3.89), 516 (3.51)
2.6 Overhauser Effect) difference spectra; this is an

NMR Spectroscopy extremely useful method for the correlation of
proton signals and has been applied to numer-
IH- and 13C-NMR spectroscopy are of unique ous lichen substances (Jakupovic and Huneck
importance for the identification and structural 1989); (3) Two-dimensional NMR spectra: (a)
elucidation of lichen substances. The following H,H COSY (Correlated Spectroscop Y) spectra,
remarks are given for scientists not so familiar which display IH chemical shifts in both
with the method. Chemical shifts (8) are in ppm dimensions, (b) H,C COSY spectra which con-
with tetramethylsilane (TMS) = 0 ppm. Signals nects IH signals in one dimension with i3C sig-
can be singlets (s), doublets (d), triplets (t), nals in the other dimension, (c) COLOC
quartets (q) or multiplets (m); broad singlets are (Correlation Spectroscopy via Long-Range
abbreviated as bs. Coupling constants are given Couplings) spectra, which are particularly suit-
in Hz. Common solvents for NMR spectroscopy able for molecules containing quarternary car-
are deuterochloroform (CDClJ, deuteroacetone bon atoms, (d) C,C COSY INADEQUATE
(CD 3-CO-CD 3, acetone-d 6), deuterobenzene (Incredible Natural Abundance DoublE
(C6 D6 ), deuterodimethylsulfoxide (CD 3 -SO- QUantum Transfer Experiment) spectra, (e)
CD 3 , DMSO-d6 ), deuteropyridine (C 6 DsN), HMBC (Proton (H) Multiple Bond Connectiv-'
deuteromethanol (CD 30D) and deuterium oxide ity) and (f) HETCOR (Heteronuclear Chemical
(D 2 0). Lichen substances are often difficult to Shift Correlation).
solve in CDCl3 or acetone-d6, and it is better to
use the corresponding methyl esters, methyl 2.6.1
ethers or acetates for the NMR spectrum. lH-NMR Spectroscopy
There are many special NMR techniques
which cannot be discussed here but should be The chemical shifts of most protons is in the
mentioned (for details see Duddeck and range between 0 and 15ppm, as demonstrated
Dietrich 1989): (1) DEPT (Distortionless En- in Table 9.
hancement by Polarization Transfer); in a 13C The IH-NMR data of depsides and
DEPT spectrum CH 3 and CH signals are positive depsidones were discussed by Huneck and
and CH2 signals negative; (2) NOE (Nuclear Linscheid (1968). The I-NMR spe.ctra of methyl
Table 9. lH-NMR shifts in lichen substances glomellate and (-)-placodiolic acid are shown in
Figs. 6 and 7, respectively.
Proton Chemical shift (in ppm)
CH 3- 0.5-2 2.6.2
-CH 2 - 1-2 13C-NMR Spectroscopy
HO-C- 1-5
CH 3-CO- 1.8-2.8 The chemical shifts of l3C-atoms in lichen sub-
CH 2-CO- 2.2-2.8
stances are in the range of 10-220 ppm. The
arom.-CH3
arom.-CH2 - 2.9-3.1 multiplicity of the signals in the coupled spec-
CH3 -O- trum gives information about the number of
3.2-4 protons at the carbon atom: =C= singlet, =C-H
CH3-0-CO- doublet, -CH 2 - triplet, and -CH3 quartet. The
-CH 2-O- 3.5-4.6
DEPT (Distortionless Enhancement by Polariza-
arom.-CH,-CO- 4-4.2
phenolic -OH 4-15
tion Transfer) method is a modern technique to
arom.-H 6.5-8.5 differentiate between CH, CH2 or CH 3 signals.
HOOC- 9-12 13C-NMR shifts oflichen substances are summa-
HCO- 9.5-10.5 rized in Table 10.
s
s
TMS
j i
I I
t 11.42 11.25
s
~
s
d
d d d
~
9 h 9 f f ed b a
------'-----------.I----~J~~/----'I------------rl-----------.1-----------.-----------.1
7 ppm 6 4 3 2 0
Fig.6. lH-NMR spectrum (200 MHz, CDCl3 ) of methyl glomellate

2.6 NMR Spectroscopy 21
11
5
1
5
h 9
~ --r-
14.38
17.90 10.36
e 5
CH3 5
5
5
0
q
TMS
f e de b a
I I
4 ppm o
Fig. 7. lH-NMR spectrum (200 MHz, CDCI 3 ) of (-)-placodiolic acid
Table 10. 13C-NMR shifts of groups present in lichens

Figure 8 demonstrates the coupled (Fig. 8a) and'
Chemical shift (in ppm)
proton-decoupled 13C-NMR spectrum of the
CH 3 - 5-30 depside pseudocyphellarin A, Fig. 9 demon-
-CH 2 - 20-40 strates the HMBC spectrum of (+ )-usnic acid,
-C- 30-50 and Fig. 10 demonstrates the HETCOR spec-
-C-H 30-60 trum of (+)-usnic acid.
-CH 2-O- 40-70
-CH-O- 60-80
The following papers deal chieilywith the !3C-
-c-o- 75-85 NMR spectroscopy of lichen substances:
arom.C 100-140 xanthol?es: Sundholm (1978a, 1979), Huneck
-Co-o- 160-180 and Haile (1978), depsides, depsidones and
COOH 170-185 depsones: Sundholm and Huneck (1980, 1981),
-CHO 180-200
and triterpenes: Wenkert et al. (1978), Wilkins
-CO- 200-230
et al. (1989b, 1990).
CHO CH3
10 ~
d qq
q
11'
C-l0
I [ I I I I
200ppm 150 100 50 o
Fig.8a,b. Coupled (a) and proton-decoupled (b) l3C-NMR spectrum (50.29 MHz, CDCI3 ) of pseudocyphellarin A
2.7 Wilkins (1979) studied the MS of di- and tri-

Mass Spectrometry oxygenated stictane triterpenoids and their
trimethylsilyl derivatives. A paper by Grigsby et
Mass spectrometry is another useful tool for al. (1974) deals with the MS of derivatives of
the identification and structural elucidation of polyporic acid, and Krause (1976) investigated
lichen substances. The principles of the the MS fragmentation of depsides, depsidones,
method are given in a review by Lehmann and usnic acid, terpenoids, fatty acids, di- and tri-
Schulten (1976). The mass spectra (MS) of glycerides and carbohydrates from lichens.
numerous depsides, depsidones, depsones, Some papers deal with the MS of usnic acid and
dibenzofuranes and diphenylbutadienes have derivatives: Kutney et al. (1974), Huneck and
been discussed by Huneck et al. (1968a). In the Schmidt (1980), and Schmidt et al. (1981). Ruef
same year, Letcher (1968) published the MS of (1990) reported on the MS of numerous lichen
some pulvinic acid derivatives. Martinez and xanthones.
Mestres (1972) recorded the MS of depsidones Holzmann and Leuckert (1990) applied the
derived from norstictic acid, and Holland and methods of negative Fast Atom Bombardment
2.7 Mass Spectrometry 23
-F2
(ppm,
J 't t t- H-13
I
1.8
1.9
-
U
2.0
1-- H-16
2.1 I
0-
2.2
U
2.3 ~
.,
2.4
U
.....
::!; <'I .....
2.5
U u U
2.6
I I
; I-H-15 / H-18
2.7
2.8
2.9
a
200 180 160 140 120 100 80 60 40 20
~~pm) H-4 - i I I
7 I/"l <'I s:l
U U U
8
10
s:
U
-
U
27.9
.I I
11
lO-OH-- I
12 0- 0
U
13 I HO OH
8-0H - -
I
14
00 .....
U U
15
H3C 0
16
17
H3C
M <'I -.,j- 31.3
18 U U U
I I
19 b J -3-0H
~F'~~
200 180 160 140 120 100 80 60 40 20
Fl (ppm)
Fig. 9. Inverse detected Long-range 'H, 13C correlation HMBC of (+)-usnic acid in CDCI,
(FAB) and MS/MS to the screening of lichen 1991). Another technique for thermically labile
substances and Tabacchi et al. (1991) analyzed substances is the field-desorption method.
lichens by tandem MS. The FAB method is a Santesson (l969b) developed a special tech-
special ionization method for organic molecules nique, the so-called lichen mass spectrometry,
which are difficult to evaporate (Hesse et al. where small fragments oflichens'are introduced
Fl -U
M Fig. 10. Heteronuclear chemical shift
correlation via IF (C,H) (HETCOR) of
---
(ppm)
1.0 M (+)-usnic acid in CDCl3
1.5
2.0
2.5
3.0
-U -U
I/') 00
3.5
4.0
--- ---
I/') 00
4.5
.q-
U
5.0
--
.q-
5.5
6.0 0
100 90 80 70 60 50 40 30 20 10
F2 (ppm)
OH Me,O I~
Me~CO-Me
1 HOO~O
~H
;;r CO
I
~
R Me
?' C
R'O ~ 0 + OH I! OH
Me~Me Me~Me
Fig. 11. MS fragmentation of depsides HOoAcH=c=o HO0~CH2
co CO
I I
Me a Me b
directly into the mass spectrometer. This
OH 0-
method works with lichens which contain only
a few compounds; otherwise the resulting Me~CO-Me
mass spectra are too complex and difficult to HOO~OH
interpret. CO
I
The main fragmentation route of depsides is Me c
the cleavage of the depside bond according to Fig. 12. MS fragmentation of usnic acid under positive and
Fig. 11. negative ionization
Table 11. Mass spectrometric fragments of lichen depsides
m/z Formula Structure mlz Formula Structure
150 CaH6 O, Me-

b.e~o
:-1+
. 166 ClO H 14 O,
HO*OM;!'
Me-
o OH Me-
1x'
151 C8 H,O, Me- Me-
CO 178 ClO H lO O3
HO OH
o~oHl'
1(?0
C..:::- O
163 C9H,O,
4 eo'
C3 H7
179 C9 H,04 Me-
Me-O :
164 C9HsO, Me- :1+
HO OH
1::(" . CHO
4'
Me-O 0 ClOHllO, Me-
h?o"
co
HO oMe-
07 COMe- Me-
4'
Me-
O*OH"
Me-
co
Mt"O OH
C..:::- o
Me-
Me- Me-
Me-
~*eo.
165 C9H 9O,
~eo.
HO OH
Me-O OH
iK
Mt"
Mt" 182 C9H lO O4
eo ' Ho~oHl'
HO OMt" COOMt"
HOyOH,
Me-
h
Mt"
192 Cll H 1,03 C3 H7
,,61'
~O'
CO
Me- :
Table 11. Continued
mlz Formula Structure mlz Formula Structure
HO*OM;J'
C3 H7 OJ t 200 CIO H 13 CIO, Me
Jx~o
o COMe Me Cl
l(
193 ClI H 13 0 3 Me
;-r
i;('"'o
CO 206 C" H ,4 0 3 CSHl1
ir
MeO OH
Me- o OH
207 C12 H1S 0 3 Me
co
~*CO'
MeO OH
'
CHO MeO o ME'
Me Me
MeO
*co' OMe
C3H7
~co.
ME' Meo OMe
Me
OHC*CO'
HO OH
ClOH 7OS
OHC*COl'
Me
HO OH
Me
Me CHO
MeO
M.*CO' OH
208 Cll H 1,04
HO~C-::-
o Or
ME'O C3H7
4 co'
Me
196 ClO H 1,04 Me 209 ClO H9 0 S Me
HO~O~'
COOMe ME'O OH
ME' COOH
199 C9 HsCI0 3 ME' 210 Cll H ,4 0 4 ME'
C'*co.
HO OH
HO*OHl'
Me COO ME'
M~ Me
Table 11. Continued
m/z Formula Structure m/z Formula Structure
Me Me
HO~OM-;]' HO*OM;l'
COOMe Me COOMe
Me Me
C1*CO'
213 C9H 6 C10 4 Me 225 CllHl30S OH
~COOH
HO OH MeO C3H7
CHO 226 Cu H ll CI0 3
220 C12 H 12 0 4 C3 H 7
~~~'
ixC~~'
o OH 234 CU H140 4
MeO
CI
:
C3 H 7
Me
lxC7~'
MeO 0
235 Cl4Hl903 C5 H"
OH
CI3 H l6 0 3 C5 H" ~~ ~CO'

ix~O Ml'O OMe
240 C12 H I6 OS OH
221 C13 H I7 0 3
MeO
C5 H,1
:
Ho:((coo;;1'
~CO' HO C5 Hl1
248 Cl4Hl604 C5 H"

HO OMl'
ix/.~'
C5 H"
;XCO' C~
Ml'O OH o OH
249 C1S H 21 0 3
ix
222 C12 H I4 0 4 OH ;:;-] f C 7 H15
HO C
70 ;XCO'
o C5 Hl1 Ml'O .. OH
Table 11. Continued The formula of an organic compound can

be calculated from high resolution MS data
mlz Formula Structure
(Beynon and Williams 1963). Substances con-
taining chlorine give characteristic isotope pat-
):;:, ~Or terns in their MS, yielding at once the number of
chlorine atoms per molecule: Fig. 13.
MeO~: CI
Table 11 contains the MS fragments of lichen
depsides and Table 12 the molecular weights
and formulae of lichen substances.
262 CSHll
2.8
O~ C~Ql' Optical Rotation
263
Meo~o C 7 H 15
Numerous lichen substances are optically ac-
tive, e.g. the well-known usnic acid, which is
found in the (+)- and (-)-form in lichens. The
Lco+ optical rotation is calculated according to the
equation
M(>O~OM(>
276 C SHll [a]T = al 100
D c.1'
CI*CO.
with [alb the specific optical rotation at the so-
HO OH dium D line (589nm) measured at the tempera-
CI ture T, at the measured optical rotation at the
wavelength of the sodium D line and the tem-
perature T, c the concentration of the solution
lCI 2CI 3CI 4CI in g/lOOml and 1 the length of the polarimeter
tube in dm (IOcm). It is necessary to give, to-
II II, III, III ,

x x+2 xx+2 xx+2 x+6 xx+2 x+6
gether with the optical rotation, the solvent used
(common solvents are CRCl3 and EtOR) and
the concentration c of the solution, e.g. (+)-
x+4 x+4 x+4 x+B
usnic acid, [a]54 + 495 (CRCl3, c 0.2).
Fig. 13. MS patterns of the molecular ion peaks of
compounds containing 1 to 4 atoms of chlorine
2.9
Optical Rotatory Dispersion (ORO)
The fragmentation of usnic acid is quite dif- and Circular Dichroism (CD)
ferent under positive and negative ionization:
Fig. 12. ORD and CD are very useful chiroptical meth-
Ion a is formed via a retro Diels-Alder pro- ods, for the characterization and determination
cess and ion b arises by a transfer of the 3-hy- of the relative and absolute configuration of
droxy hydrogen to C-4. Contrary to the positive chiral compounds. Their application was re-
ion MS, the negative one shows only a [M- viewed by Snatzke (1968,1981, 1982). ORD data
CR 3 ] - peak corresponding to ion c. are given either as [an with [a] the specific
Molecular Weights and Formulae of Lichen Substances 29
Table 12. Molecular weights and formulae of lichen substances
Molecular weight Formula Lichen substance
26 C,H 4 Ethylene
94 C,H 6O,S Dimethyl sulfone
116 C6H 1,06 Caproic acid
116 C4H,04 Fumaric acid
118 C4H 60 4 Succinic acid
122 C7 H 6O, Benzoic acid
122 C4H IO O4 meso-Erythritol
124 C7H,O, Orcinol
125 C,H 7 N0 3S Taurine
130 C7H 14O, Oenanthic acid
134 CIO H 14 p-Cymene
136 CIOH 16 Camphene
136 C lO H 16 Limonene
136 C lO H 16 Myrcene
136 C lO H 16 (X-Pinene
136 C lO H 16 ~-Pinene
138 C,HlOO, Orcinol mono methyl ether
138 C,HlOO, ~-Orcinol
144 C8H160 , Caprylic acid
150 CsHIOOs Arabinose
150 C IO H 14O Carvone
152 CSH120S Arabitol
152 C,H S 0 3 Atranol
152 C lO H 16 O Camphor
152 C9 H 1,O, Divarinol
152 C,H 12 O, Orcinol dimethyl ether
152 C9H 12 O, ~-Orcinol monomethyl ether
152 CSH 12 O, Ribitol
152 C lO H 16O (X-Thujone
152 C lO H 16O ~-Thujone
154 C lO H 18O Borneol
154 ClO H 18 0 1,8-Cineol
154 C lO H 1BO Fenchol
154 ClO H 18 0 Linalool
154 C IO H 1,O Terpinen -4-01
154 CIOH 180 (X-Terpineol
158 C4H 6N40 3 Allantoin
163 C6 H 13 NO; Xantholamine
166 C lO H 14 O, Divarinolmonomethylether
166 C,H 60 4 Phthalic acid
168 CBHsO, Orsellinic acid
175 ClO H 9NO, Indolyl-3-acetic acid
180 C,H,04 5,7 -Dihydroxy-6-methylphthalide
180 C6H 12 0 6 Fructose
180 C6H 12 0 6 Galactose
180 C6H 12 0 6 Glucose
180 C6H 12 0 6 myo-Inositol
180 C l1 H 16O, Olivetol
Table 12. Continued
180 C6 H I2 0 6 Tagatose
182 C6H l4 0 6 Mannitol
182 C.H 10 0 4 Methyl orsellinate
182 C9H lO 0 4 ~-Orcinolcarboxylic acid
183 CsH I3 N0 4S Cholin sulphate
186 CBH 7CI0 3 Chloroatranol
194 Cl2HIS02 Olivetolmonomethylether
196 C IO H I2 0 4 4,6-Dihydroxy-2-methoxy-3-methylacetophenone
196 C lO H I2 0 4 Divaric acid
196 C lO H 1,04 Ethyl orsellinate
196 C9HBOS Haematommic acid
196 ClO H l2 0 4 Methyl ~-orcinolcarboxylate
196 C7H l6 0 6 Siphulitol
206 Cll H lO 0 4 Eugenitol
210 Cll H l4 0 4 Ethyl everninate
212 C7H l6 0 7 Volemitol
220 C12 H 12 0 4 Eugenitin
222 CllHlOOS Graphisquinone
224 CllH120S Ethyl haematommate
224 C29 H 60 O N onacosan-1 0-01
224 Cl2Hl604 Olivetolcarboxylic acid
234 CIsH2202 Fukinanolide
236 C12 H 12 OS 6-Hydroxymethyleugenitin
238 C13 H 1S 0 4 Ethyl divaricatinate
238 CI3 H 1S 0 4 4-0-Methylolivetolcarboxylic acid
240 CI7H" n-Heptadecane
240 Cll H.CI0 4 Sordidone
242 C1s H 30 O, Pentadecanoic acid
246 Cl4Hl404 Graphenone
250 C I2 H lO 0 6 1,4,5,8-Tetrahydroxy-3-ethylnaphtho-2,6-q uinone
254 C is H lO 0 4 Chrysophanol
256 Cl6H3202 Palmitic acid
258 Cl4HlOOS Norlichexanthone
266 C1s H n 0 4 EthyI4-0-methylolivetolcarboxylate
270 C1sHlOOS Emodin
270 C1sHlOOS Islandicin
270 C1sHlOOS Strepsilin
272 C l4 H 8 0 6 Canarione
272 C1SH12OS Hypostrepsilic acid
272 C1SHI2OS 3-0-Methylnorlichexanthone
272 C1SHI2OS 6-0-Methylnorlichexan thone
272 C I2 H I6 0 7 Montagnetol
272 ClsHIZOS Norascomatic acid
272 CZO H 3, Rimuene
272 Cl6Hl604 Trypethelone
274 C l4 H lO 0 6 Simonyellin
280 C1sH 32 O, Linoleic acid
282 C1s H 34 O, Oleic acid
Table 12. Continued
284 C1s H s0 6 Emodinaldehyde

284 CI6H12OS Parietin
284 CIsH3602 Stearic acid
286 C1s H lO O6 Alectosarmentin
286 C,sH lO O6 Citreorosein
286 C'SH'OO6 Cynodontin
286 Cl6Hl40S Lichexanthone
286 Cl6Hl40S 6-0-Methylnorascomatic acid
286 C,sH lO O6 1,5,6,8-Tetrahydroxy-3-methylanthraquinone
286 Cl7Hl804 Trypethelone methyl ether
288 C12 H 12 0 6 1,8-Dihydroxy-3,6-dimethoxyxanthone
289 C13 H,oN04Cl Sticticin
290 C2o H 34 O (-)-ent-Kauran-16a-ol
290 C2o H 34 O Manool
290 C1sH lO O4 Pulvic acid lactone
290 C1s H II ClO4 1,6,8-Trihydroxy-3-methyl-7 -chloro-1 O-anthrone
292 Cl 4H9ClO s 2-Chloronorlichexanthone
292 Cl4 H9 ClO s 4-Chloronorlichexanthone
292 C'4H9ClOs 5-Chloronorlichexanthone
292 Cl 4H9ClO s 7-Chloronorlichexan thone
292 C1S H 120 4 Polyporic acid
292 C'3 H SO, 3,6,3' ,6'-Tetrahydroxy-4-methyl-biphenyl-2,5,2' ,5'-diquinone
296 C17 H 28 0 4 Acarenoic acid
296 C'7 H 28 0 4 Nephrosterinic acid
296 C,oH 40 0 4 Phytol
297 C,sH 23 NO s Solorinin
298 C'7 H 30 0 4 Acaranoic acid
298 C'6H lO O6 Fallacinal
298 C'7H 30 0 4 Lactone carboxylic acid from Lecanora rupicola
298 C'7 H30 0 4 Nephrosteranic acid
300 C'7Hl60S Ascomatic acid
300 C'SH,07 Emodic acid
300 Cl6H'2 0 6 Erythroglaucin
300 C'6 H ,,06 Fallacinol
300 C'7H'60S Methyl 6-0-methylnorascomatate
300 C'7 H ,,04 Roccellic acid
300 C'6 H 12 0 6 Xanthorin
302 C,sH lO O7 Asahinin
302 C'SH'OO7 1,4,5,6,8-Pentahydroxy-3-methylanthraquinone
302 C,oH 30 0 2 Sandaracopimaric acid
304 C,sH 9ClO s 7-Chloroemodin
304 C,sH 120 7 Haemoven to sin
306 C18H,oOs Calycin
306 C,sHIIClOs 2-Chloro-3-0-methylnorlichexanthone
306 C,sHIIClO s 2-Chloro-6-0-methylnorlichexanthone
Table 12. Continued
306 C1sHllCIO s 7-Chloro-3-0-methylnorlichexanthone

306 C1sHllCIO s 7-Chloro-6-0-methylnorlichexanthone
306 C1sHllCIOs 2-Dechlorothiomelin
306 C1sHllCIO s 4-Dechlorothiomelin
306 C1BHlOOS 2-Hydroxypulvic acid lactone
306 C1sHllCIO s 1-Methoxy-4-chloro-5,8-dihydroxy-6-methylxanthorre
306 ClsHllCIO s Vinetorin
307 CIBH 13 NO. Pulvinamide
308 CIBHl20S Pulvinic acid
310 Cl,H'60S Portentol
312 ClgH'6 0 , Lichesterylic acid
314 Cl6 H lO O, Endocrocin
314 CllHnO lO 1-0-p-D-Galactopyranosyl-D-ribitol
314 Cl6 H lO O, Haematommone
314 ClsHIBOS Methyl ascomatate
314 CI,H I.06 N ordechloropannarin
314 C l6 H lO O, Parietinic acid
314 C l6 H lO O, Porphyrilic acid
314 C ll H 2,OlO Umbilicin
314 C l6 H lO O, Variolaric acid
316 ClgH 2.04 Bis-(2,4-dihydroxy-6-n-propylphenyl)-methane
316 ClsH200S 8-Methoxytrypethelone methyl ether
316 C16 H 12O, Pannaric acid
318 C16 HllCIO s 7-Chloro-1-0-methylemodin
318 C16 HllCIO s Fragilin
318 C16Hl407 Isolecanoric acid
318 C l6 H l4 O, Lecanoric acid
318 C16 HllCIO s 1-0-Methyl-7-dichloroemodin
318 C1sHlOOS Rhodocladonic acid
318 C1sHlOOS 2,5,7 -Trihydroxyemodin
320 C16 H13CIO s 2-Chlorolichexanthone
320 CI 6H13ClO s 7-Chlorolichexanthone
320 CI 6H13CIO s 2-Dechloro-8-0-methylthiomelin
320 C16H13CIO s 4-Dechloro-8-0-methylthiomelin
320 C16H 13 CIO s 1,5-Dimethoxy-4-chloro-6-methyl-8-hydroxyxanthone
320 C ls HgC10 6 Papulosin
322 ClgH 140 S Vulpinic acid
324 C19H 32 0 4 allo-Protolichesterinic acid
324 C1gH'2 0 4 Lichesterinic acid
324 ClgH'2 0 4 Protolichesterinic acid
325 ClsHIOCI,O. 1,7 -Dihydroxy-2,4-dichloro-6,8-dimethylxanthone
326 C17 H IO O, Biruloquinone
326 ClgH'4 0 Nephromopsinic acid
326 ClgH,.O. Roccellaric acid
327 Cl4HsCl20s 2,4-Dichloronorlichexanthone
327 Cl 4HsCI,Os 2,5-Dichloronorlichexanthone
Table 12. Continued
327 Cl 4HsCI,Os 2,7 -Dichloronorlichexanthone

327 Cl 4HsCI,Os 4,5-Dichloronorlichexanthone
327 Cl 4HsCI,Os Northiomelin
328 Cl9H3604 Angardianic acid
328 CI 8H 32 OS Aspicilin
328 Cl8H1606 Dechloropannarin
328 C17 H 12 0 7 Methyl porphyrilate
329 C1 4HlOCI,Os Chlorovinetorin
330 Cl7H1407 4-0-Demethylnotatic acid
330 C17H'4 0 7 Didechlorolecideoidin
330 Cl7H1407 9-Methyl pannarate
330 C17H'4 0 7 IS-Methyl pannarate
330 C17H I4 0 7 3-0-Methylpannaric acid
330 C17H1407 8-0-Methylpannaric acid
330 C'7H 140 7 Norisonotatic acid
330 C17H1407 Nornotatic acid
330 C17H1407 Subnotatic acid
332 C17H1607 Alectorialin
332 C17 H13CIO s 2,7 -Dimethoxy-3-methyl-5-hydroxy-6-chloroanthraquinone
332 C17 H'6 0 7 Evernic acid
332 Cl8 H,006 4' -Hydroxy-8-methoxytrypethelone methyl ether
332 C17 H'6 0 7 Isonorobtusatic acid
332 C'7H13CIOs 1-0-Methylfragilin
332 C1 7H13CIO s 8-0-Methylfragilin
332 C17H1607 Methyllecanorate
332 C17H1607 Norobtusatic acid
334 C1sH lO 0 9 Chiodectonic acid
334 C16H140S Diploschistesic acid
334 C1 6 H'40S S-Hydroxylecanoric acid
334 C16 H ll Cl0 6 1-0-Methyl-7 -chlorocitreorosein
334 C17HlSCIOs 1,5,8-Trimethoxy-2-chloro-6-methylxanthone
338 C'9 H 140 6 Demethylleprapinic acid
338 C19H1406 1,8-Dihydroxy-6-methoxy-3-(3'-oxo-but -1' -enyl)-anthraquinone
338 C'9 H 14 0 6 4-Hydroxyvulpinic acid
338 C'OH340 4 Methyl protolichesterinate
339 C1sHsCI,d s 5,7 -Dichloroemodin
339 C16 H 12CI,04 1-Hydroxy -2,4-dichloro-6,8-dimethyl-7 -methoxyxanthone
341 C1sHlOCI,Os 2,4-Dichloro-3-0-methylnorlichexanthone
341 C1sH,oCI,Os 2,5-Dichloro-3-0-methylnorlichexanthone
341 ClsHIOCl,Os 2,5-Dichloro-6-0-methylnorlichexanthone
341 C,sHIOCI,Os 4,5-Dichloro-3-0-methylnorlichexanthone
341 C1SHlOCI,Os 4,5-Dichloro-6-0-methylnorlichexanthone
341 C1sHlOCI,Os 4,7 -Dichloro-3 -0-methylnorlichexanthone
341 C1sHlOCI,Os 4,7 -Dichloro-6-0-methylnorlichexanthone
Table 12. Continued
341 ClsHlOCI,Os 5,7 -Dichloro-3-0-methylnorlichexanthone

341 ClsHlOCI,Os 5,7-Dichloro-6-0-methylnorlichexanthone
341 ClsHlOCI,Os Dinorscensidin
341 ClsHlOCl20S Thiomelin
341 ClsHlOCI,Os Thiophaninic acid
342 C18Hl407 Monoacetylfallacinol
342 C'OH'20S Subdidymic acid
342 C12H"Oll Sucrose
342 C12 H"Oll Trehalose
344 C17H 12 0 8 2' -0-Demethylpsoromic acid
344 C18H1607 3-0-Demethylschizopeltic acid
344 C12 H'4 0 11 3-0-~-D-Glucopyranosyl-D-mannitol
344 C18H1607 Hypoprotocetraric acid
344 ClsH1607 Hypopsoromic acid
344 C18H1607 Isonotatic acid
344 Cl8H1607 Isousnic acid
344 ClsH1607 9-MethyI8-0-methylpannarate
344 ClsH1607 Notatic acid
344 C12 H'4 0 11 Peltigeroside
344 ClsH1607 Usnic acid
346 C17H140S Barbatolin
346 ClsHlS07 4-0-Demethylbarbatic acid
346 Cl8HlS07 Isooptusatic acid
346 C18Hl807 Methyl evernate
346 ClsHl807 3'-Methylevernic acid
346 C18HlS07 2'-0-Methylevernic acid
346 C17H1 4OS 9-MethyI4-hydroxypannarate
346 C18HlS07 Methyl 3'-methyllecanorate
346 C18H1807 2' -0-Methylnorobtusatic acid
346 C18 H IS 0 7 Obtusatic acid
348 ClsHl7CIOs 5-Dechlorovicanicin
348 C I7 H 13 CI0 6 Norpannarin
348 C18H3604 Sativic acid
352 C19 H 28 0 6 Acetylportentol
352 C'OH l60 6 Leprapinic acid
352 C'OH l60 6 Pinastric acid
352 C19 H 12 0 7 Russulone
352 C1SHSOg Thelephoric acid
354 C,oH lS 0 6 Averythrin
354 C21H3804 Lactone carboxylic acid from Cladonia impexa
354 C19H1407 Nemetzone
354 C21 H 19 CI0 3 N ostoclide II
354 C2oH'2 N,04 Picroroccellin
355 C16H12C120s 3-0-Demethylscensidin
355 C1 6H12CI,Os 2,4-Dichlorolichexanthone
355 C1 6H12CI,Os 2,5-Dichlorolichexanthone
355 C16H12C120s 2,7 -Dichlorolichexanthone
355 C16Hl,Cl20S 4,5-Dichlorolichexanthone
Table 12. Continued
355 CI6H'2ClzOs 4,7 -Dichlorolichexan thone

355 CI 6H, 2Cl,Os 5,7 -Dichlorolichexanthone
355 C16H12C120s 8-0-Methylthiomelin
356 C22 H 42 OS Bourgeanic acid
358 C21H260S Brialmontin 2
358 CZOH2206 Hyponephroarctin
358 Cl8Hl40S Hyposalazinic acid
358 C1,H1SO, Isoschizopeltic acid
358 C1,H 34 0 6 Jackinic acid
358 C I9 H ,SO, 4-0-Methylhypoprotocetraric acid
358 C,sH'40S Psoromic acid
358 C" H 18O, Schizopeltic acid
358 ClsH140S Virensic acid
360 C1,H 20 O, Barbatic acid
360 Cl8Hl60S Conhypoprotocetraric acid
360 ClsH'60S Convirensic acid
360 C18 H 16 0 8 4-0-Demethylbaeomycesic acid
360 C1,H 20 O, 4-0-Demethyldiffractaic acid
360 C1,H 20 O, Evernin
360 C1,H 20 O, Methyl 4-0-demethylbarbatate
360 C I9 H 20 O, 2'-0-Methylnorbarbatic acid
360 C1,H,oO, 2-0-Methylobtusatic acid
360 C18H'60S Ramalinaic acid
360 C19 H 20 O, Subdivaricatic acid
361 C14 H 7CI 3Os Arthothelin
361 C14 H,CI,os Asemone
361 C14H7Cl30s Concretin
361 C14 H,CI,os 2,4,5-Trichloronorlichexanthone
361 C, 4 H,CI 3Os 2,4,7 -Trichloronorlichexanthone
361 C, 4 H,CI 3Os 2,5,7 -Trichloronorlichexanthone
361 C14 H,CI 3Os 4,5,7 -Trichloronorlichexanthone
362 ClsH'80S Lepraric acid
362 C'9HI9CIOs 4-0-Methyl-5-dechlorovicanicin
362 C18 H 15 CI0 6 Pannarin
364 C" H 13 CIO, 3'-Dechlorolecideoidin
364 C2IH 32 OS Neuropogolic acid
366 C2,H'S06 Leprapinic acid methylether
366 C2lH340S Muronic acid
366 C2IH 34 OS Neuropogonic acid
366 C2lH340S Isomuronic acid
366 C18 H 'S ONa Sodium usneate
368 C2lH360S Constipatic acid
368 C2lH360S Dihydropertusaric acid
368 CZIH2006 6-0-Methylaverythrin
368 C21 H 36 OS Murolic acid
368 C21H360S Neuropogolic acid
368 C21H360S Protoconstipatic acid
369 C"H, 4 CI,Os Fulgoicin
Table 12. Continued
369 C17H1 4 Cl,Os N orvicanicin

369 Cl 7H1 4 Cl,Os Scensidin
370 C21 H,,06 Conorlobaridone
370 C"H'60S Didymic acid
370 C22 H'60S Isodidymic acid
370 C"H'60S Melacarpic acid
370 C21H3S0S (-)-2-Methylene-3(R)-carboxy-18(R)-hydroxynonadecanoic acid
370 C21 H 3S OS Neodihydromurolic acid
370 C,oH 1S 0 7 Norsolorinic acid
370 C,sH 3S O, Retigeranic acid A
370 C,sH 3S O, Retigeranic acid B
372 C'OH'007 Averantin
372 C"H,sOs Brialmontin 1
372 C19H160S Hypostictic acid
372 C19Hl60S Methyl vir ens ate
372 C'OH'007 Nephroarctin
372 C'OH360 6 Norrangiformic acid
372 C1sH 1,09 Norstictic acid
372 C'OH360 6 Pseudonorrangiformic acid
372 C1s H 1,09 Substictic acid
374 C19H1SOS Atranorin
374 C19H1SOS Baeomycesic acid
374 ClsHl409 Connorstictic acid
374 C,oH 22 0 7 4-0-Demethyldivaricatic acid
374 C,oH 22 0 7 Diffractaic acid
374 C18 H 140 9 Menegazziaic acid
374 C'OH,,07 Methyl barbatate
374 C,oH22 0 7 Nordivaricatic acid
374 C1SH 140 9 Protocetraric acid
375 C15H9Cl3OS 6-0-Methylarthothelin
375 ClsH9Cl30S 3-0-Methylasemone
375 ClsH9Cl30S 6-0-Methylasemone
375 C1sH,Cl3OS Thuringione
375 C15H,Cl3OS 2,4,7 -Trichloro-3-0-methylnorlichexanthone
375 C15H,Cl3OS 2,4,7 -Trichloro-6-0-methylnorlichexanthone
375 C1sH,Cl3OS 2,5,7-Trichloro-3-0-methylnorlichexanthone
375 C1s H 9Clps 2,5,7 -Trichloro-6-0-methylnorlichexanthone
375 C1sH 9Cips 4,5,7 -Trichloro-3-0-methylnorlichexanthone
376 C18H1609 Alectorialic acid
376 C18H1609 Conprotocetraric acid
376 C18 H 160 9 Decarboxythamnolic acid
376 ClsHl609 4-0-Demethylsquamatic acid
376 Cl9 H,oOs 8-Hydroxybarbatic acid
376 C1,H,oOs Methyl 8-hydroxy-4-0-d'emethylbarbatate
376 C1,H l7 Cl0 6 4-0-Methylpannarin
376 C1sH 13Cl0 7 Phyllopsorin
376 C19 H'008 Placodiolic acid
376 Cl9 H,008 Pseudoplacodiolic acid
Table 12. Continued
378 Cl8HlsCI07 3-Dechlorogangaleoidin

380 Cl8Hl7CI07 5-Chloro-4-0-demethylbarbatic acid
380 Cl8 H 17 CI0 7 Methyl 5-chloronorobtusate
380 Cl8 H 17CI0 7 Wrightiin
382 C2lH3406 19-Acetoxylichesterinic acid
382 C2lH3406 19-Acetoxy-protolichesterinic acid
382 C27 H42 O Cholesta-3,5-dien-7-one
382 C21 H 34 0 6 Praesorediosic acid
382 C2l H 34 0 6 Protopraesorediosic acid
383 Cl 8Hl 6CI,Os Isovicanicin
383 Cl.Hl6Cl20S Vicanicin
383 C17 H 12 CI20 6 Eriodermin
383 C l7 H l,CI,06 N orargopsin
384 C21 H 20 0 7 Solorinic acid
386 C2,H 42 OS Bourgeanic acid
386 C27 H46 O Cholesterol
386 C2l H 22 0 7 Divaronic acid
386 C2l H,,06 Isorangiformic acid
386 C21 H,,07 6-0-Methylaverantin
386 C21 H 3.06 Rangiformic acid
386 Cl9Hl409 Stictic acid
388 C27H 4S O Cholestan-3~-ol
388 Cl9Hl609 Cryptostictic acid
388 C21 H'4 0 7 Divaricatic acid
388 C2,H 2.06 Homoheveadride
388 Cl9Hl609 Hypoconstictic acid
388 C2oH2008 2' -O-Methylatranorin
388 C'lH'4 0 7 2-0-Methylnordivaricatic acid
388 C2o H 36 0 7 Norcaperatic acid
388 ClgH 12 OlO Salazinic acid
388 C'lH'4 0 7 Subsphaeric acid
389 Cl6HllCl30s 3-Dechlorodiploicin
389 Cl6HllCl30s Fulgidin
389 Cl6HllCl30s Isofulgidin
389 C2lHlgCl203 N ostoclide I
389 Cl6HllCl30s 2,4,5-Trichlorolichexanthone
389 Cl6H ll CI,07 2,4,7 -Trichlorolichexanthone
389 Cl6H ll CI,07 2,5,7 -Trichlorolichexanthone
389 Cl6HllCl307 4,5,7 -Trichlorolichexanthone
390 ClsHl4010 Barbatolic acid
390 Cl8Hl40l0 Consalazinic acid
390 C2oH'2 0 8 8-H ydroxydiffractaic acid
390 C2o H 22 0 8 Leprolomin
390 Cl,H l8 0 9 Squamatic acid
390 C20H220g Subsekikaic acid
391 Cls H,Cl 30 6 Demethylchodatin
392 C2.H 40 O Ergosta -4,6,8,11,22- penta en- 3~-ol
392 CI9 H l7 CIO? Hypophysciosporin
Table 12. Continued
394 C2s H 42 O Ergosta -5,7,9(11 ),22-tetraen -3 ~-ol

394 C'8 H 42 0 Ergosta-5,7,14,22-tetraen -3~-ol
394 C19H19Cl07 Methyl 5-chloro-4-0-demethylbarbatate
396 C18H14Cl206 Argopsin
396 C2s H 44 O Ergosta-3,5-dien-7 -one
396 C2s H 44 O Ergosta-5,7,9(11)-trien-3~-ol
396 C2s H 44 O Ergosterol
396 C2s H 44 O Lichesterol
396 C14H6Cl40s Thiophanic acid
397 ClsHl4Cl206 Allorhizin
397 C18 H 14 Cl,06 Argopsin
397 C17H12Cl207 Lecideoidin
397 C1 9H1 8 Cl,Os 4-0-Methylvicanicin
398 C'SH46O Brassicasterol
398 C'4H300S Condidymic acid
398 C'SH46O Episterol
398 C2s H 46 O Ergosta-7,22-dien-3~-ol
398 C28 H 46 O Ergosta -7 ,24(28 )-dien -3 ~-ol
398 C28 H 46 O Fecosterol
398 C'3 H 26 0 6 Iso-norlobaridone
398 C17 H 1,Cl,O, Lecideoidin
398 C'SH46O 4a-Methyl-23-dehydrolophenol
398 C'3 H '6 0 6 Norlobaridone
399 C17 H 1,Cl,O, Norgangaleoidin
400 C28 H 4S O Campesterol
400 C22 H'4 0 , 4-0-Demethylgrayanic acid
400 C28 H 48 O Ergost -5-en -3 ~-ol
400 C,sH 4S O Fungisterol
400 C20H1609 Methylstictic acid
401 C17 H 14Cl,O, Methyl 3,5-dichlorolecanorate
402 C21 H 3S O, Caperatic acid
402 C'OH180 9 Cetraric acid
402 C19H14010 Constictic acid
402 C"H26O, 4-0-Demethylimbricaric acid
402 C22H'6 0 , 4-0 -Demethylsphaerophorin
402 C22 H 26 O, 4-0-Demethylstenosporic acid
402 C20HlS09 4,2' -Di-O-methylconnorstictic acid
402 C'lH 22 lDs Isopseudocyphellarin A
402 C28 H SO O 24~-Methylcholestan-3~-ol
402 C22 H'6 0 , 2-0-Methyldivaricatic acid
402 C22 H'6 0 , 2' -0-Methyldivaricatic acid
402 C21 H 22 OS Pseudocyphellarin A
402 C19H14010 Siphulellic acid
403 C17 H 13CI 3 O, Caloploicin
403 C17 H 13CI3 OS 3-Dechloro-4-0-methyldiploicin
403 C17 H 13 CI3 O, Tri -0-methylarthothelin
404 C21 H,.Os 4' -0-Demethylsekikaic acid
404 C'OH'009 Elatinic acid
'fable 12. Continued
404 Cl9Hl60IO Haemathamnolic acid

404 C21H 24 OS 4'-0-Methylnorsekikaic acid
404 C2o H,009 2-0-Methylsquamatic acid
404 CZIH240S Pseudocyphellarin B
404 C21H'40S Subpaludosic acid
404 C"H 44 0 6 Tetrahydroxy fatty acids
406 Cl9HISC108 Chlorogranulatin
406 C,oH l9 CI0 7 l' -Chloronephroarctin
406 Cl9HISCIOs Cydographin
406 Cl9Hl8010 Hypothamnolic acid
406 C,oH l9 CI0 7 4-0-Methylhypophysciosporin
406 Cl9HISCI08 Physciosporin
406 Cl9HISOIO Prunastric acid
407 C19HISCIOs Chlorogranulatin
407 Cl9HISCIOs Physciosporin
408 Cl9Hl7CIOs Chloroatranorin
408 C,oH 21 CIO, Methyl eriodermate
408 C'9 H44 0 Stigmasta-3,5,22-trien-7 -one
410 C'9 H 46 0 24S-Methylergosterol
410 C19 H,,01O Methyl gyrophorate
410 ClsH8Cl40s 3-0-Methylthiophanic acid
410 ClsH8Cl40s 6-0-Methylthiophanic acid
410 CI9 H,,0IO Mollin
410 C'9 H 46 0 Stigmasta-3,5-dien-7 -one
410 C30 H SO Taraxer-14-ene
411 C I8 H l2 CI,07 Chlorophyllopsorin
412 C'9 H 4S 0 30-Nor-21a-H-hopan-22-one
412 C'9 H 48 0 Poriferasterol
412 C'9 H 48 0 Stigmast-4-en-3-one
412 C29 H48 O Stigmasterol
413 C 1s H l4 CI,07 Gangaleoidin
413 C l8 H l4 Cl,O, Leoidin
414 C'9 H SO O Clionasterol
414 C'9 H SO O 24S -Ethylcholest -7 -en-3~-01
414 C21 H 26 0 7 Grayanic acid
414 C23 H'6 0 , Iso subpicrolichenic acid
414 C"H"Os Methyl8-hydroxybarbatate
414 C'9 H SO O ~-Sitosterol
414 C"H'6 0 , Stenosporonic acid
414 C'9 H SO O Stigmast -7 -en-3~-01
414 Cn H'6 0 , Subpicrolichenic acid
414 C21 H I8 0 9 Vesuvianic acid
416 C"H'40S 4-0-Demethylloxodellic acid
416 C'3 H '8 0 , 2,2' -Di-O-methyldivaricatic acid
416 C'9 H S'O 24S -Ethylcholestan -3~-ol
416 CIsH28013 O-a- D-Galactopyranosyl-( 1-76)-0-~- D-galactopyranosyl-( 1-71)-D-glyceritol
416 C'3 H '8 0 , Imbricaric acid
416 C"H,sO, Isosphaeric acid
Table 12. Continued
416 C22H 24 OS 2'-0-Methyl-iso-pseudocyphellarin A

416 Cn H'S07 2-0-Methylnorimbricaric acid
416 Cn H'S07 2-0-Methylnorstenosporic acid
416 C22 H'4 0 S 2' -0-Methylpseudocyphellarin A
416 Cn H 2s 0 7 Norlobariol
416 C21 H'009 Phenarctin
416 C'OH'60 ,O Physodalic acid
416 C'3 H 'S07 Sphaerophorin
416 C'3 H 'S07 Stenosporic acid
417 C,sH,sCl,os Buellolide
418 C'OH'8 0 10 Conphysodalic acid
418 C22 H'6 0 S Contortin
418 C22H'6 0 S 2,4'-Di-0-methylnorsekikaic acid
418 C22 H'6 0 S meta-Scrobiculin
418 C'2H 26 0 S para-Scrobiculin
418 C'2 H '6 0 8 Sekikaic acid
418 C'2 H '6 0 S Submerochlorophaeic acid
420 C'9 H '6 0 11 Thamnolic acid
422 C21 H'3 Cl0 7 3-Chlorodivaricatic acid
422 C21 H'3 Cl0 7 5-Chlorodivaricatic acid
422 C21 H'3 Cl0 7 Methyl 2-0-methyleriodermate
422 C2l H'3 Cl0 7 Methyl 4-0-methyleriodermate
422 C21 H n Cl0 7 Methyl 2' -O-methyleriodermate
424 C'6HIOCl"OS Diploicin
424 C30 H 4S O a-Amyrone
424 C30 H 4S O f3-Amyrone
424 C,sH 3,N,04 Arthonin
424 C'6HIOCl40S Diploicin
424 C30 H 4S O Hop-21 13- H -22(29)-en-3-one
424 C30 H 4S O Isomultifiorenone
424 C30 H 4S O Lupeone
424 C30 H 4S O Moretenone
424 C"HzoO s Orcinyllecanorate
424 C30 H 48 O Taraxerone
426 C30HSOO a-Amyrin
426 C30HSOO f3-Amyrin
426 C30HSOO Friedelin
426 C22 H'8 0 9 Isidiophorin
426 C'6H340S Isohyperpicrolichenic acid
426 C30HSOO Lanosterol
426 C30HSOO Lupeol
426 C'9 H 46 0 , 30-Nor-21a-H-hopan-3,22-dione
426 C'4 H '6 0 7 Siphulin
426 C30HSOO Taraxerol
427 C,sH"Cl,Os Methyl 5,1' -dichloronorpsoromate
428 C'3H'40S Conloxodin
428 C,sH44 0 3 Ergosterol- 5a,8a- peroxide
428 C'9 H 4S 0 2 Fremontol
:rable 12. Continued
428 C30 H s2 O Friedelan-3~-ol

428 C2gH48 O, 3 ~- Hydroxy-30-nor -hopan -22-one
428 C23 H24 OS Loxodellonic acid
428 C24H'8 0 , Norcolensoic acid
430 C21 H 18O lO a-Acetylhypoconstictic acid
430 C'OH140 11 a-Acetylsalazinic acid
430 C24H300 , Anziaic acid
430 C'8 H 46 0 3 Cerevisterol
430 C23 H'6 0 8 Loxodellic acid
430 C'4 H 30 0 , 2-0-Methylstenosporic add
430 C'4H 30 0 , 2' -O-Methylstenosporic acid
430 C'4 H 30 0 , 2'-0-Methylimbricaric acid
430 C'4 H30 0 , 2-0-Methylnorstenosporic acid
430 C'2 H22 0 9 2'-0-Methylphenarctin
430 C'4 H30 0 , N orlobariolmethylpseudoester
430 C23 H26 0 8 Oxostenosporic acid
431 C17 H ll CIO, Chloroleddeoidin
432 C23 H,sOs Congrayanic acid
432 C'4 H48 0 6 6-Ethyl-6-n -pen tyl-pentadecan -4,5, 7,8,15-pen tol-I5-acetate
432 C23H2808 4' -0-Methylnorhomosekikaic acid
432 C23 H,s08 2-0-Methylsekikaic acid
432 C23 H'8 0 S Methyl sekikate
432 C'3 H '8 0 8 Paludosic add
432 C23 H 28 0 8 Ramalinolic acid
433 C1sH,sCI30 6 Buellolide
435 C25 H,sN0 6 Epanorin
436 CnH,sCIO, Methyl 2,2' -di-O-methyleriodermate
438 C,oHnO ll Erythrin
438 Clo H46 0, Fern-9( 11 )-en-3, 12-dione
438 C17 H"CI4 Os 4-0-Methyldiploicin
440 Cn H 2oN,08 4,4'-Diacetylscabrosin
440 C30 H 48 O, 3~-Hydroxyolea-12-en-ll-one
440 C'6 H 32 0 6 2' -0-Methylphysodone
441 C'9 H '4 C1 ,Os Methyl 5,1' -dichloropsoromate
442 C,sH 30 O, Colensoic acid
442 C30 H so O, Fern-9(ll)-en-3~,12a-diol
442 C30 H so O, Fern-9( 11)-en-3~,12~-diol
442 C30 H so O, 22a-Hydroxy-3,4-secostict-4(23)-en-3-al
442 C30 H so O, 22a-Hydroxystictan-3-one
442 C'4H'60S Oxysiphulin
442 C"H30O, Picrolichenic acid
442 C30 H so O, Zeorinone
444 C21 H'6 0 11 a-Acetylconstictic acid
444 C'4H2S0S 4-0-Demethylglomelliferic acid
444 C30 H s,O, 6-Deoxyleucotylin
444 CnH'OOll 8' ,9' -Di-O-ethylsalazinic acid
444 C,sH 3,O, 2,2' -Di-O-methylimbricaric acid
444 C25 H 3,O, 2,2' -Di-O-methylstenosporic acid
Table 12. Continued
444 C30Hs20Z Hopan-7~,22-diol

444 C30HszOz Hopan-15a,22-diol
444 C30HSOOZ Hopan-16~,22-diol
444 CZS H32 0 7 2-0-Methylanziaic acid
444 CZSH3Z07 2'-0-Methylanziaic acid
444 CZ3H400S MethyI3,4-dicarboxy-3-hydroxy-19-oxo-eicosanoate
444 C24 H2SOS Normiriquidic acid
444 C2s H32 0 7 Perlatolic acid
444 C24H2S0S Protosiphulin
444 CSOHS202 Stictan-3~,22a-diol
444 C30H5202 Zeorin
445 C18HllCl307 Erythrommone
445 ClsHllCl307 2,4,5-Trichloro-3,6-di-0-acetylnorlichexanthone
446 C24H34N206 Arthogalin
446 C24H300S Homosekikaic acid
446 C24H3008 Isomerochlorophaeic acid
446 C24H3008 Merochlorophaeic acid
446 C24H300S 4' -O-Methylpaludosic acid
448 C29Hs203 Hierridin
450 C23H27C107 3-Chloroimbricaric acid
450 C23 H27 CI0 7 3-Chlorostenosporic acid
452 ClsH14Cl40S Canesolide
452 C21 H24 0 11 Roc.cellin
456 C2sH280S Glomelliferonie acid
456 C2s H 28 OS Lobaric acid
456 C2s H 28 OS Loxodin
456 CSOH4S03 Ursolic acid
458 Cz4 H26 O, 4-0-Demethylglomellic acid
458 CZ6H3407 4-0-Demethylplanaic acid
458 C26 H340 7 2,2' -Di-O-methylanziaic acid
458 C2sH300S Glomelliferic acid
458 C2sH3008 3-Hydroxycolensoie acid
458 C30 HS003 3~-Hydroxyhopan-29-oic acid
458 C30 HS003 22a-Hydroxy-3,4-secostict-4(23)-en-3-oic acid
458 CZS H30 0 S Isopatagonie acid
458 C26H3407 2-0-Methylperlatolic acid
458 C26H3407 2' -O-Methylperlatolic acid
458 C2s H30 1D 8 Miriquidie acid
458 C2sH300S Patagonie acid
458 CSO HS003 Phlebie acid B
458 CSO HS003 Phlebie acid C
460 C25H3208 Boninie acid
460 C2sH3208 Cryptochlorophaeic acid
460 C30Hs20S Hopan-6a,7a,22-triol
460 CSOHS20S Leucotylin
460 C21 H 16 0 12 Malonprotocetraric acid
460 C2sH3208 Methyl merochlorophaeate
460 C25H3208 4' -O-Methylnorcryptochlorophaeie acid
Table 12. Continued
460 C30Hs203 Stictan -2a,3 ~,22a- triol

466 C22H26011 Galapagin
468 C24 H 24N,08 4-Acetyl-4'-butyryl-scabrosin
468 C32HS20, Acetyl-iso-arborenol
468 C32 H s,O, Acetyltylolupenol B
468 C18H14Cl406 Canesolide
468 C24H20010 Gyrophoric acid
468 C'7 H 32 0 7 Haemophaein
469 C28H'3 N0 6 Rhizocarpic acid
470 C27 H 34 0 7 Hyperpicrolichenic acid
470 C27H3407 3-0-Methyllividic acid
470 C26 H 30 0 8 Physodic acid
472 C31Hs203 Acetyl-a-tocopherol
472 C"H 160 12 Fumarprotocetraric acid
472 C,sH 2S 0 9 Glomellic acid
472 C27 H 36 0 7 Hyperlatolic acid
472 C29H3,N204 Hypothallin
472 C27H3607 Isohyperlatolic acid
472 C26H320S 3-Methoxycolensoic acid
472 C26 H 32 OS 2-0-Methylglomelliferic acid
472 C'6 H 32 0 , Olivetoric acid
472 C27H3607 Planaic acid
472 C30H4S04 Retigeric acid A
472 C26H3208 Subconfiuentic acid
474 C22H18012 Confumarprotocetraric acid
474 C30HS004 6a,22-Dihydroxyhopan-23-oic acid
474 C30HS004 16~,22-Dihydroxyhopan-23-oic acid
474 C26H340S Epiphorellic acid I
474 C'6H340S Hyperhomosekikaic acid
474 C30HS004 Leucotylic acid
474 C2sH3009 Loxodinol
474 C26H340S 4-0-Methylcryptochlorophaeic acid
474 C26H340S 4'-0-Methylcryptochlorophaeic acid
474 C26H340S 4-0-Methylisocryptochlorophaeic acid
474 C30HS004 Pyxinic acid
474 Cn H 18 0 12 Succinprotocetraric acid
476 C"H'OO12 Consuccinprotocetraric acid
476 C30HS,04 Pyxinol
478 C2sH31Cl07 3-Chloroperlatolic acid
482 C32 H S0 0 3 3~-Acetoxyfern-9(11)-en-12-one
482 C2s H 2,OlO 4-0-Methylgyrophoric acid
482 C2s H n O IO 2"-0-Methylgyrophoric acid
482 C'SH'2 0 10 Ovoic acid
482 C'SH'2 0 10 U mbilicaric acid
484 C3,H s,03 3~- Acetoxyfern-9( 11 )-en-12~-ol
484 C3,H s,03 3~- Acetoxyfern-9( 11 )-en-19~-ol
484 C"HS20 3 12a-Acetoxyfern-9(11 )-en-3~-ol
484 C24H,oOll Crustinic acid
Table 12. Continued
484 C24H,oOll Hiascic acid

484 C27H"Os 4-0-Methylphysodic acid
484 C27H320S 2' -0-Methylphysodic acid
486 C"HS40 3 6a-Acetoxyhopan -22-01
486 C"H540 3 7~-Acetoxyhopan-22-01
486 C32Hs403 15a-Acetoxyhopan-22-01
486 C32 H 54 0 3 16~- Acetoxyhopan -22-01
486 C32 H 540 3 3-Acetoxy-3,4-secostict-4(23 )-en -22a-01
486 C32Hs403 3 ~- Acetoxystictan -22a-01
486 C"HS40 3 16~-0- Acetyl-6-deoxyleucotylin
486 C26H3009 3-Hydroxyphysodic acid
486 C2sH3S07 2-0-Methy1hyperlatolic acid
486 C2sH3S07 2' -0-Methylhyperlato1ic acid
486 C28 H 38 O, 2-0-Methylisohyperlatolic acid
486 C2sH3S07 2' -0-Methy1isohyperlatolic acid
486 C27H3408 4-0-Methylolivetoric acid
486 C26H3009 Vittato1ic acid
488 C27 H 36 0 8 4,4'-Di-O-methylcryptochlorophaeic acid
488 C'6H ,,09 Epiphorellic acid II
488 C"HS60 3 3-H ydroxy-5-methyl-4,6-dimethoxy-2- (tricos-9' -eny1)-benzene
488 C26 H 32 0 9 4-0-Methyl-2"-oxo-cryptoch1orophaeic acid
488 C31Hs204 Methyl pyxinate
488 C28H32N404 Roccanin
490 C'SH260 9 G1omellonic acid
494 C23 H'6 0 12 Lobodirin
496 C'6 H '8N 20 8 4-Acetyl-4' -hexanoy1scabrosin
496 C'6 H 28N 20 8 4,4'-Dibutyry1scabrosin
496 C26H24010 2,4-Di-0-methy1gyrophoric acid
496 C26H24010 4,2"-Di-0-methylgyrophoric acid
496 C'6 H U O IO Tenuiorin
498 C'4 H 1SO l' 7,7' -Bis- (1,4,5,8-tetrahydroxy-3-ethy1naphtha-2,6-quinone)
498 C,sH"On 3-Hydroxyumbilicaric acid
498 C,sH"On 2-0-Methy1hiascic acid
498 C,sH"On 4-0-Methylhiascic acid
498 C,sH"On 5-0-Methy1hiascic acid
498 C,sH"On 2' -0-Methy1hiascic acid
498 C'9 H 3S 0 , Superpicrolichenic acid
500 C3,H s1 0 4 25-Acetoxy-20( S),24(R)-epoxydammaran-3-one
500 C28 H 36 0 S Confluentic acid
500 C29H 40 O, Hyperp1anaic acid
500 C29H4007 Isohyperp1anaic acid
500 C27 H 32 0 9 Lividic acid
500 C29H4007 2-0-Methy1norsuperlato1ic acid
500 C29H4007 Micareic acid
500 C29 H 40 O, Prasinic acid
502 C32 H 54 0 4 25-Acetoxy-20(S),24(R)-epoxydammaran-3~-01
502 C32 H 54 0 4 3 ~- Acetoxyhopan -1 ~,22-dio1
502 C"H540 4 6a-Acetoxyhopan-7a,22-dio1
T.able 12. Continued
502 C 32 H s4 0 4 6a- Acetoxyhopan-16~,22-diol

502 C32H 54 0 4 7a-Acetoxyhopan-6a,22-diol
502 C3,H 54 0 4 16~- Acetoxyhopan-6a,22-diol
502 C32 H 54 0 4 20a-Acetoxyhopan-6a,22-diol
502 C32 H 54 0 4 2a-Acetoxystictan -3 ~,22a-diol
502 C32 H 54 0 4 3-Acetoxystictan-2a,22a-diol
502 C32 H 54 0 4 6-0-Acetylleucotylin
502 C27 H 34 0 9 ~-Alectoronic acid
502 C30H4606 Retigeric acid B
510 C27H26010 2-0-Methyltenuiorin
510 C27H26010 2' -O-Methyltenuiorin
510 C27H26010 2"-0-Methylten uiorin
512 C28 H 32 0 9 a-Alectoronic acid
512 C,sH 32 0 9 ~-Alectoronic acid
512 C'6 H 24 0 11 4,5-Di-0-methylhiascic acid
512 C32 H 64 O. 1-(O-a-D-Glucopyranosyl)-3( S),25 (R) -hexacosanediol
512 C26H24011 3-Methoxyumbilicaric acid
513 C2s H 30 CI,07 3,5-Dichloro-2' -O-methylanziaic acid
514 C2sH3409 4-0-Demethylmicrophyllinic acid
514 C29H'80S 2-0-Methylconfiuentic acid
514 C29H3S0S 4-0-Methylhyperolivetoric acid
514 C30H4207 2-0-Methylsuperlatolic acid
514 C30 H.20 7 2'-0-Methylsuperlatolic acid
516 C'2 H S2 0 S 15a-Acetoxy-22-hydroxyhopan-24-oic acid
516 C32Hs20S 16-0-Acetylleucotylic acid
516 C32Hs20S Aipolic acid
516 C32Hs20S Phlebic acid A
516 C32Hs20S Phlebic acid D
518 C32Hs40S 3-0-Acetylpyxinol
524 C28 H 2S O lO 2,2"-Di-O-methyltenuiorin
526 C'9 H 34 0 9 a-Collatolic acid
526 C2.H 34 0 9 ~-Collatolic acid
526 C31H4207 Isomegapicrolichenic acid
526 C31H4207 Megapicrolichenic acid
526 C27H26011 3-Methoxy-2,4-di-0-methylgyrophoric acid
526 C27H26011 2,4,5-Tri-O-methylhiascic acid
527 C26H32Cl207 2-0-Methylsulphurellin
528 C29H3609 Arthoniaic acid
528 C34Hs604 3 ~,22a- Diacetoxystictane
528 C30H400S Hyperconfiuentic acid
528 C29H3609 Microphyllinic acid
528 C31 H 44 0 7 Superplanaic acid
530 C,oH 42 O. Methoxymicareic acid
530 C'3 H S4 0 S Methyl 3-0-acetylpyxidate
536 C4o H s6 a-Carotene
536 C4o H s6 ~-Carotene
536 C4o H 56 y-Carotene
538 C2sH26011 2-0-Acetyltenuiorin
Table 12. Continued
538 C30H'8 0 10 Skyrin

540 C27 H 24 O" 5-0-Acetyl-4-0-methylhiascic acid
540 CJOH3609 2'" -0-Ethyl-f3-alectoronic acid
542 CJ,H 4,O, 4-0-Demethylsuperconfiuentic acid
542 CJ4 H 54 OS 2a,3f3-Diacetoxystictan-22-one
542 CJOH22010 Graciliformin
542 C30H3S09 2'-0-Methylmicrophyllinic acid
542 C3,H42 0 8 4-0-Methylsuperolivetoric acid
542 C30H'2 0 10 Rugulosin
544 C34Hs60S 6a, 1613-Diacetoxyhopan-22-01
544 CJ4HS60S 2a,3 13-Diacetoxystictan -22a-ol
544 C34Hs60S Diacetyl-12-deoxypyxinol
544 CJ4Hs60S 6a, 1613-Diacetylleucotylin
546 CJOH'6 0 10 Isohypocrellin
550 C4oH s4 O Echinenone
552 C4o H s4 O f3-Cryptoxanthin
552 C28H24012 Furfuric acid
554 C30H'8 0 11 Oxyskyrin
556 CJ2 H 44 O S Superconfiuentic acid
560 CJ.H S6 0 6 Diacetylpyxinol
564 C4oHs202 Canthaxanthin
568 C4oHs602 Lutein
568 C4o H 56 0 2 Zeaxanthin
570 CJ2H4207 2' -0-Methylhyperphyllinic acid
570 C30H,sO'2 Skyrinol
573 C30H'4C1208 7,7~-Dichlorohypericin
584 C40 H s6 0 3 Antheraxanthin
584 C33H4409 2' -0-Methylnorsuperphyllinic acid
584 C32H24011 Monoacetylgraciliformin
584 C4oHs603 Mutatoxanthin
584 C4oHs603 Taraxanthin
586 C33 H 46 0 9 2'-0-Methylsuperphyllinic acid
586 C36HSS06 2a,3f3,22a-Triacetoxystictane
596 C4oH s2 O, Astaxanthin
598 C3.H46 O, Glaucophaeic acid
600 C4o H 56 0 4 Neoxanthin
600 C4o H s6 O. Violaxanthin
613 CJoH19Cl308 Flavoobscurin A
618 CJOH so 0 13 Hexa - (a-hydroxyisovalerate)
620 CJ9Hs606 5a,8a-Peroxyergosteryl divaricatinate
626 CJ4H2;0" Diacetylgraciliformin
631 C4,H 74 0 4 1,1-Dimethylnoneicosyl everninate
638 CJ2H30O'4 Ergochrome AA
638 C32H30O'4 Ergochrome AB
642 C30H12C140s 2,2',7,7'-Tetrachlorohypericin
646 C34H30013 Aphthosin
648 C30 H IS Cl4 0 s Flavoobscurin B,
648 C30H'8Cl.08 Flavoobscurin B,
660 C3,Hs,O'4 Lepranthin
666 C34H J4O'4 Eumitrin A2
666 C34H34O'4 Eumitrin B
680 C34 H J,O,s Eumitrin A,
766 C42H38O'4 4,4'-Disolorinic acid
876 CS7H9S06 Glyceryl trilinolate
2.11 Thin Layer Chromatography 47
optical rotation at the wavelength X and the 7. Solvents for extraction: acetone, ethanol or
temperature T or as the molecular rotation [] diethyl ether
8. Reagents for microcrystallization:
GAW: H 20: glycerol: ethanol = 1: 1: 1 (v/v/v)

GE: acetic acid: glycerol = 1 : 3
with M the molecular weight of the correspond- An: aniline: glycerol: ethanol = 1 : 2: 2
ing compound. The molecular ellipticity [8] of oT: 0- toluidine: glycerol: ethanol = 1 : 2 : 2
the CD is interconnected with the differential Py: pyridine: glycerol: water = 1 : 1 : 3
dichroic absorption L1E = EL - ER by the equation Q: quinoline: ethanol: glycerol = 1 : 2 : 2.
KK: 5 g KOH + 20 g K2 C0 3 in 100 ml H20
[8] = L1E 3300.
Procedure. A piece of the lichen is extracted
The absolute configuration of numerous ali- with acetone (or ethanol or diethyl ether), the
phatic lichen acids was determined by their CD solution filtered through a small funnel equipped
spectra: Huneck and Follmann (1967), Huneck with a small ball of cotton wool and the solvent
et al. (1979), Huneck and Snatzke (1980b), of the extract evaporated. The residue is trans-
Huneck and H6fle (1980), Huneck et al. (1983, ferred with a spatula or a scalpel to a microscope
1986), and Huneck and Takeda (1992). slide, a drop of the proper reagent placed on the
deposit and covered with a cover glass. The slide
2.10 using GE or GAW is heated carefully over the
Microcrystallization micro flame and set aside for cooling and crys-
tallization, which in some cases requires several
The micro crystallization of lichen substances hours. The slides with the other reagents are
was developed mainly by Asahina (1936-1940) normally not heated. The crystals are best ob-
and Asahina and Shibata (1954). The microcrys- served in polarized light under 100-400-fold
tal test can be performed on a microscope slide magnification. The substances can be identified
with a high degree of accuracy and speed. The by the crystal shape and colour. Photographs of
substances are identified by their characteristic selected microcrystals of lichen substances are
crystal formation in various reagents. Because presented in the Figs. 14-67 and the crystal
of its simplicity, the method is rapidly accepted character of the corresponding compounds is
by lichenologists and has been used for chemo- briefly described in Table l3.
taxonomic work on lichens.
For the microcrystal test the following acces- 2.11
sories are necessary: Thin Layer Chromatography
1. Microscope equipped for polarized light Thin layer chromatography (TLC) is now the
2. Small test tubes (0.8 x 6cm) method of choice for the rapid determination
3. Small pipettes (5-10) of 1-2ml capacity and and identification of lichen substances, and nu-
0.5 cm inner diameter merous,papers have been published on this sub-
4. Micro spirit-lamp or micro Bunsen-burner ject. Santesson (1967) reported the Rf values of
5. Spatula or scalpel about 80 lichen substances, and Yoshimura and
6. Microscope slides (2.5 x 8 cm) and cover Kurokawa (1977) investigated the sensitivity of
glasses (1.8 x 1.8cm) TLC for several lichen substances: lecanoric
Table 13. Comments to the microcrystals of lichen substances
Figure
14A Mixture of acaranoic and acarenoic acids: short fan-shaped lamellae
14B, C Caperatic acid: globular branched masses
14D Lichesterinic acid: small rectangular lamellae
lSA Norrangiformic acid: radiating clusters of thin lamella or needles
lSB Protolichesterinic acid: exceedingly thin square-like rhombic plates which form
ladder-like patterns
lSC Pseudonorrangiformic acid: small needles in radiating masses; in small clusters the crystals
may form branching needles with the tendency to curve in the same direction
ISD Rangiformic acid: clusters of thin lamellae or needles
16A Roccellic acid: clusters of short needles
16B Roccellaric acid: very thin rectangular lamellae
16C Aspicilin: large plate-like lamellae
16D Alectorialic acid: clusters of needles
17A Alectorialic acid:bright yellow spindle-shaped crystals
17B Alectorialic acid: coarse yellow prisms
17C Anziaic acid: clusters oflong and narrow, often curved needles; easily soluble in GE
17D,18A Atranorin: elongate rhombic prisms
18B, C Atranorin: clusters of curved yellow needles
18D Atranorin: fine needles
19A Baeomycesic acid: small yellow crystals
19B Baeomycesic acid: boat-shaped thin plates
19C Baeomycesic acid: pale rhombic thin plates
19D Barbatic acid: small rhombic prisms
20A Barbatic acid: long needles
20B Barbatic acid: delicate thin lamellae
20C Barbatolic acid: aggregates of small rod-shaped crystals
20D Boninic acid: small hexagonal or ellipsoid plates
21A Chloroatranorin: fine needles
21B, C Chloroatranorin: feathery clusters of curved fine yellow needles
2iD,22A Chloroatranorin: fine needles
22B Confiuentic acid: long curved needles
22C Confiuentic acid: brushy long needles
22D Confiuentic acid: fine needles
23A Cryptochlorophaeic acid: long curved needles which radiate out from condensation
nuclei, forming hair-like masses
23B, C, D, 24A 4-0-Demethylbarbatic acid: lamellae
24B, C Diffractaic acid: aggregates of long narrow lamellae with curved ends
24D,2SA Diffractaic acid: long prisms
2SB Diploschistesic acid: long curved narrow lamellae with fine needles
2SC Divaricatic acid: at first aggregates of needles, then criss-cross needles
2SD Erythrin: brushy fine needles
26A Evernic acid: feathery clusters of more or less curved needles
26B, C Glomelliferic acid: crystals with brushy needles at both ends
26D Glomelliferic acid: rod-like prisms
27A Gyrophoric acid: clusters of fine curved crystals
27B Haemathamnolic acid: rectangular prisms
27C Haemathamnolic acid: needles
27D Haemathamnolic acid: narrow boat-shaped lamellae
28A Hiascic acid: aggregates of narrow lamellae
28B Homosekikaic acid: prisms
Microcrystallization 49
Table 13. Continued
28C, D Hypothamnolic acid: small rhombic crystals

29A Imbricaric acid: large needles
29B, C, D Lecanoric acid: thin curved needles
30A Lecanoric acid: prisms
30B,C Merochlorophaeic acid: elongate fiat lamellae
30D Microphyllinic acid: radiating needles
3IA Miriquidic acid: aggregates of narrow lamellae with acute ends
3IB Nephroarctin: small rectangular prisms
31C, D Obtusatic acid: needles
32A Obtusatic acid: rhombic plates
32B, C Olivetoric acid: thin curved needles
32D Perlatolic acid: clusters of crystals
33A Perlatolic acid: long needles
33B Planaic acid: thin curved needles
33C Ramalinolic acid: aggregates of rhombic prisms
33D meta-Scrobiculin: long needles
34A Sekikaic acid: rectangular prisms
34B Sekikaic acid: rhombic plates
34C, D Sphaerophorin: long needles
35A Squamatic acid: rhombic prisms
35B Tenuiorin: fine needles
35C Thamnolic acid: boat-shaped yellow plates
35D Thamnolic acid: aggregates of yellow needles
36A Tumidulin: fine curved fibres
36B Tumidulin: needles
36C Umbilicaric acid: rectangular prisms
36D, 37A, B a-Alectoronic acid: long lamellae
37C Colensoic acid: aggregates oflamellae
37D a-Collatolic acid: aggregates of lamellae
38A Constictic acid: aggregates of minute rod-like prisms
38B Diploicin: needles
38C Fumarprotocetraric acid: short prisms
38D Fumarprotocetraric acid: clusters of short yellow needles
39A Grayanic acid: radiating clusters of needles
39B Hypoprotocetraric acid: fiat plates or thick prisms
39C Hypoprotocetraric acid: clusters of needles
39D Hypoprotocetraric acid: thin curved needles
40A Lobaric acid: clusters of thick rhombic needles
40B Loxodin: rhombic lamellae
40C, D 4-0-Methylphysodic acid: prisms
41A, B Norlobaridone: clusters of fine needles
4IC Norstictic acid: red needles
41D Norstictic acid: pale yellow lamellae
42A Norstictic acid: clusters of yellowish long lamellae
42B Norstictic acid: boat shaped lamellae
42C Pannarin: clusters of colourless needles which modify to aggregates of yellowish lamellae after
a day
42D Psoromic acid: curved colourless needles which modify into a yellow powder after a few days
43A Psoromic acid: clusters of yellowish needles
43B Psoromic acid: tiny crystals
43C Protocetraric acid: small needles
Table l3. Continued
43D Protocetraric acid: small yellow warts

44A,B Physodic acid: flat curved needles
44C,D,45A Physodalic acid: rod-like prisms
45B Physodalic acid: radiating masses of fine needles
45C Salazinic acid: dark red curved needles
45D Salazinic acid: yellow boat-shaped lamellae
46A Salazinic acid: clusters of lamellae
46B Stictic acid: regular hexagonal lamellae
46C Stictic acid: hexagonal lamellae with rounded margins
46D Virensic acid: aggregates of slightly curved needles
47A Vir en sic acid: curved fine needles
47B Virensic acid: small needles
47C Picrolichenic acid: rhombic or hexagonal prisms
47D,48A Didymic acid: clusters of rhombic needles
48B Isousnic acid: yellow prisms
48C Isousnic acid: pale yellow crystals
48D Placodiolic acid: rectangular plates
49A, B Porphyrilic acid: long curved needles
49C Schizopeltic acid: clusters of needles
49D Strepsilin: rhombic plates or prisms
50A, B Usnic acid: yellow prisms or needles
SOC Galapagin: needles
SOD Galapagin: thin plates
5IA Galapagin: needles
SIB Lepraric acid: rectangular thin plates
SIC Lobodirin: long rod-iike crystals
5ID,52A Roccellin: long straight crystals
52B Sordidone: long needles
52C Sordidone: aggregates of plates
52D Sordidone: long needles
53A Lichexanthone: needles
53B Thiophanic acid: pale yellow narrow lamellae
53C Thiophanic acid: rhombic plates
53D Thuringione: pale yellow needles
54A Thuringione: pale yellow rods
54B (-)-ent-Kauran-16 a-ol: long fine crystals
54C (-)-ent-Kauran-16 a-ol: needles
54D,55A 7~-Acetoxyhopan-22-ol: long straight crystals
55B, C, D Hopan-15 a, 22-diol: rhombic prisms
56A Frieqelin: long lamellae
56B Leucotylin: long needles
56C Leucotylin: long rhomboid prisms
56D Retigeric acid A: long straight fine needles
57A Retigeric acid B: granules
57B Ursolic acid: minute rods or needles
57C Ursolic acid: long rods or prisms
57D Zeorin: double pyramids
58A Bellidiflorin: brownish hexagonal plates
58B Materia rubra: clusters of red needles
58C Dissectic acid: brownish rhomboid prisms
2.12 High Performance Liquid Chromatography 51
Table 13. Continued
58D a-Acetylsalazinic acid: straight crystals

59A a-Acetylsalazinic acid: small granules
59B, C Placodiolic acid: clusters of needles
59D, 60A, B Bourgeanic acid: radiating clusters of needles
60C, D Acetylportentol: rhombic, hexagonal or octagonal prisms
61A, B (-)-2-Methylene-3(R)-carboxy-18(R)-hydroxynonadecanoic acid: fan-shaped lamellae
61C Neodihydromurolic acid: thin"1amellae
6ID,62A Nephrosteranic acid: very thin rhombic plates which form ladder-like patterns
62B, C 2-0-Methylconfiuentic acid: long slender needles
62D 3,5-Dichloro-2'-O-methylanziaic acid: long hair-like needles
63A 3,5-Dichloro-2'-O-methylanziaic acid: small rhombic prisms
63B 3,5-Dichloro-2'-O-methylanziaic acid: long hair-like needles
63C, D Gangaleoidin: rods
64A Gangaleoidin: clusters of needles
64B, C 3-Hydroxycolensoic acid: rhombic double pyramids
64D 3-Hydroxycolensoic acid: rod-like crystals
65A, B Ergosterol: irregular lamellae
65C ~-Sitosterol: rod-like crystals
65D ~-Sitosterol: irregular plates
66A Evernin: aggregates of needles
66B, C Pseudoplacodiolic acid: hexagonal prisms
66D Pseudoplacodiolic acid: aggregates of needles
67A, B Methoxycolensoic acid: prisms
67C Arthothelin: straight crystals
67D 2,4-Dichloroxanthone: small rods
acid: 0.0025/lg, lobaric acid: 0.005/lg, zeorin: (1979). Bendz et al. (1967) were able to separate
O.oq.lg, usnic acid: 0.16/lg and vulpinic acid: the antipodes of usnic acid by TLC after heating
0.3 /lg. A standardized TLC method for the iden- with brucine.
tification of lichen products was developed by Table 14 contains data on TLC solvent sys-
c.P. Culberson and coworkers: c.P. Culberson tems used in lichen chemistry and Table 15 data
and Kristinsson (1970), C.P. Culberson (1972b, on reagents and other methods for the visualiza-
1974), c.P. Culberson and Ammann (1979), C.P. tion of the TLC spots.
Culberson et al. (1981), c.P. Culberson and Like many other methods, TLC has its limits,
Johnson (1982). A useful supplement for mix- and the results should be interpreted critically;
tures that are difficult to separate is the two- it is risky to identify a lichen substance by one Rf
dimensional TLC described by c.P. Culberson value only. The Rf values of the lichen sub-
and Johnson (1976). Renner and Gerstner stances are mentioned in the special part (Part
(1978b) described the TLC of lichen substances, 3) of this book.
and White and James (1985) gave much advice
for the TLC identification of lichen metabolites. 2.12
High performance thin layer chromatography High Performance Liquid
(HPTLC) is an improved technique for screen- Chro'matography (HPLC)
ing lichen substances (Arup et al. 1993). Purther
data on the TLC of lichen substances are given High performance liquid chromatography
by Bach-mann (1962), Ramaut (1963a,b, (HPLC) is a method for the anglysis of com-
1967a,b), Ramaut et al. (1978) and Chawla et al. pounds which cannot be separated by gas liquid
Table 14. Solvent systems used in the TLC oflichen substances
Solvent system Suitable for the separation of:
Toluene: dioxane: acetic acid = 90: 25: 4" (standard solvent A) All lichen substances
n-Hexane: diethyl ether: formic acid = 5: 4: 1 (standard solvent B)
Toluene: acetic acid = 85: 15 (standard solvent C)
Toluene: ethyl acetate: formic acid = 139: 83: 8 (standard solvent G) ~-Orcinol depsidones
n-Hexane: methyl tert.-butyl ether: formic acid = 140: 72: 18 All lichen substances
Toluene: diethyl ether: acetic acid = 3 : 6 : 1 Aromatic aldehydes
Toluene: diethyl ether: acetic acid =7: 12: 1 "
Cyclohexane: chloroform: methyl ethyl ketone = 30: 15: 2 Atranorin, chloroatranorin, pannarin
Diethyl ether: acetic acid = 50: 1 Erythrin, gyrophoric acid, lecanoric acid
Carbon tetrachloride: methyl ethyl ketone: acetic acid = 6: 2: 1 Dibenzofuranes
Toluene Quinones
Toluene: cyclohexane = 4: 1 "
Chloroform: acetone = 4: 1 Pulvinic acids and usnic acid
n-Hexane: chloroform: acetone = 2: 3: 1
n-Hexane: chloroform: acetone = 10: 8: 1
Chloroform Xanthones and chromones
Dichloromethane: acetone = 4: 1
Benzene: dioxane: acetic acid = 90: 25: 4 (Pastuska mixture) All lichen substances
Chloroform: methanol = 24: 1 Terpenoids
Benzene: ethyl formiate: formic acid = 25: 25: 3 (silica gel H impregnated Polar quinones
with 0.5% ethylene-diamine tetraacetic acid)
Benzene (silica gel PF 254 + 366, impregnated with 0.5M oxalic acid) Placodiolic acid
Benzene: methanol = 7: 3 (silica gel G, impregnated with chlorobenzene Pulvinic acids
vapours)
"All values in volume.
Table 15. Reagents for the visualization of TLC spots of lichen substances
Reagent Suitable for the identification of:
UV light (with plates containing a fluorescence indicator, e.g. Merck Most lichen substances
Silica gel PF 254 + 366)
Iodine vapour, 15 min at room temp. All lichen substances, brown spots
20% Sulphuric acid, 15min at 150C All lichen substances, grey, brown, blue spots
10% Chlorosulphonic acid in acetic acid, 15 min at 150C All lichen substances, different-coloured
spots, terpenoids violet
0.5 ml Anisaldehyde + 1.0 ml sulphuric acid + 8.5 ml methanol, Depsides and usnic acid, red to blue-violet
10min 100-110C
5% p-Phenylenediamine in ethanol Aromatic aldehydes, yellow to orange to red
2% Magnesium acetate in ethanol Quinones, pink to violet
Diazotized benzidine + NaOH (solution A: 2.5g benzidine + 7ml' Depsides, depsidones and
conc.HCI in 500ml H2 0; solution B: 50g NaN0 2 in 500ml H20; Phenolic cleavage products, red
equal volumes of A and B are mixed immediately before the
application of the reagent)
Fig. 14. A Mixture of acaranoic acid and acarenoic acid, GE. Bar 100 Ilm. B Caperatic acid, GE. Bar 100 Ilm. C Caperatic
acid, GE. Bar 10 Ilm. D Lichesterinic acid, GE. Bar 10 Ilm
,
1\
,,//'
., . .. I
"
J"
.'
,
..
..
,
....
.'
"' .... 0'
.. '
o
Fig. 15. A Norrangiformic acid, GE. Bar 100 11m. B Protolichesterinic acid, GE. Bar IOOl1m. C Pseudo-norrangiformic
acid, GE. Bar 10 11m. D Rangiformic acid, GE. Bar 100 11m
,
'j
.~
-
"
-
0 -. -
'.." , .--
--
:.--
8
Fig. 16. A Roccellic acid, GE. Bar 100 /lm. B Roccellaric acid, GE. Bar 100 /lm. C Aspicilin, GE. Bar 10 /lm. D Alectorialic
acid, GE. Bar 100 /lm
1\
,.-:
L-.
(0;> t"
\)
A
I
Fig. 17. A Alectorialic acid, oT. Bar 10 11m. B Alectorialic acid, Q. Bar 10 11m. C Anziaic acid, GE. Bar 10 11m. D Atranorin,
GE. Bar 10 11m
,.-
I
\
o
Fig. 18. A Atranorin, GAW. Bar lOO~m. B Atranorin, oT. Bar lOO~m. C Atranorin, oT. Bar lO~m. D Atranorin, Q.
Bar lOO~m
.A L
1 ..
~
-'..' ""1S
'
to" , I
t
.I-
..
7.:'
'"
.
~
I
.'-
,.
-
~
yJ.
.
~ .J
'
A i
'-'"
...
..... B
,.,
'Il
I
o
Fig. 19. A Baeomycesic acid, a 5% solution of o-anisidine in glycerol: ethanol = 1 : 1. Bar 100 11m. B Baeomycesic acid, An.
Bar 100 11m. C Baeomycesic acid, Q. Bar 100 11m, D Barbatic acid, GE. Bar 10 11m
Fig. 20. A Barbatic acid, oT. Bar 100 JlID. B Barbatic acid, Py. Bar 100 JlID. C Barbatolic acid, Py. Bar 10 JlID. D Boninic
acid, GE. Bar 10 JlID
Fig. 21. A Chloroatranorin, GE. Bar 10 /.lm. B Chloroatranorin, oT. Bar 100/.lm. C Chloroatranorin, oT. Bar l0/.lm.
D Chloroatranorin, An. Bar 100 /.lm
Fig. 22. A Chloroatranorin, Q. Bar 10 11m. B Confiuentic acid, GE. Bar 10 11m. C Confluentic acid, Py. Bar 100 11m.
D Confluentic acid, oT. Bar 10 11m.
r
/
I
c D
Fig. 23. A Cryptochlorophaeic acid (from Cladonia cryptochlorophaea Asah.), GE. Bar 100 11m. B 4-0-Demethylbarbatic
acid, GE. Bar 100 11m. C 4-0-Demethylbarbatic acid, Q. Bar lOOl1m. D 4-0-Demethylbarbatic acid, Py. Bar 10 11m.
Fig. 24. A 4-0-Demethylbarbatic acid, Py. Bar 100 !lm. B Diffractaic acid (from Usnea diffracta Vain.), GE. Bar 100 !lm.
e Diffractaic acid, GE. Bar 10 !lm. D Diffractaic acid, Py. Bar lOO!lm
..,
,.
lr- - ,
;.~
~ ~\ I
C
~
Fig. 25. A Diffractaic acid, Py. Bar 10 11m B Diploschistesic acid, GE. Bar 1001lm. C Divaricatic acid, GE. Bar 100 11m.
D Erythrin, GE. Bar 10ilm
_/ A B
o
Fig. 26. A Evernic acid, GE. Bar 100~m. B Glomelliferic acid, GE. Bar 100~m. C Glomelliferic acid, GE. Bar 10~m. D
Glomelliferic acid, Py. Bar 100 J,lm.
.,~ .. ~~
,:.
/.- -."..
.""
.,- "
Fig. 27. A Gyrophoric acid, GE. Bar 10 /lm. B Haemathamnolic acid, GE. Bar 10 /lffi. C Haemathamnolic acid, saturated
aqueous solution of Ba( OH)2' Bar 100/lm. D Haemathamnolic acid, An. Bar 100 /lm
/ .
c / I
,#

o
Fig. 28. A Hiascic acid, GE. Bar 100 ~m . B Homosekikaic acid (from Cladonia ramulosa (With.) Laundon), oT.
Bar 100 ~m. C Hypothamnolic acid (from Cladonia pseudostellata Asah.), GE. Bar 100 ~m. D Hypothamnolic acid, GE.
Bar lO~m.
4
\
.,
I
I'.
I
o
Fig. 29. A Imbricaric acid [from Cetrelia cetrarioides (De!. ex Duby) W. Culb. et C. Culb.)] GE. Bar 100 11m. B Lecanoric
acid, GE. Bar 100 11m. C Lecanoric acid (from Parmelia tinctorum Ny!.), GE. Bar 100 11m. D Lecanoric acid, GE. Bar 10 11m.
Fig. 30. A Lecanoric acid, Q. Bar 100 11m. B Merochlorophaeic acid (from Cladonia merochlorophaea Asah.), GE. Bar
100 11m. C Merochlorophaeic acid, GE. Bar 10 11m. D Microphyllinic acid [from Cetrelia japonica (Zahlbr.) W. Culb., et C.
Culb.] GE. Bar 100 11m.
.\
... i
~ .
~
~ ~
rJi.
B
I
,. . ~
Fig.31. A Miriquidic acid [from Stereocaulon commixtum (Asah.) Asah.], GE. Bar 10 /-lm. B Nephroarctin, An. Bar 10 /-lm.
C Obtusatic acid, GE. Bar 100/-lm. D Obtusatic acid, GE. Bar 10/-lm.
Fig.32. A Obtusatic acid, Q. Bar 100 11m. B Olivetoric acid, GE. Bar 100 11m. C Olivetoric acid, GE. Bar 10 11m. D Perlatolic
acid, GE. Bar 100 11m.
Fig. 33. A Perlatolic acid, Q. Bar 10 11m. B Planaic acid, GE. Bar 10 11m. C Ramalinolic acid with sekikaic acid (from
Ramalina peruviana Ach.), GE. Bar 10 11m. D meta-Scrobiculin, GE. Bar 10 J.lm
A
, ,
--
c
Fig. 34. A Sekikaic acid, GE. Bar 100/lm. B Sekikaic acid, oT. Bar 10/lm. C Sphaerophorin, GE. Bar 100/lm. D
Sphaerophorin, GE. Bar 10/lm
;:I
--
Fig. 35. A Squamatic acid [from Cladonia crispata (Ach.) Flot.], GE. Bar 10/-1m. B Tenuiorin, GE. Bar 100/-lm. C
Thamnolic acid, saturated aqueous solution of Ba(OH)2' Bar lO0/-lm. D Thamnolic acid with decarboxythamnolic acid,
An. Bar 100/-lm
., <:
,
\0 ~
t:>
..
.
~
'-. 7 .. /
~ .. .
g'.
..
0 C
lit
Fig. 36. A Methyl 3,5-dichlorolecanorate, GE. Bar 100 11m. B Methyl 3,5-dichlorolecanorate, Py. Bar 10011m.
e Umbilicaric acid, GE. Bar 100 11m. D a-Alectoronic acid, GE. Bar 100 11m
,

.
~ ~I
.. ~,. t~;;'
~~~
.,
.......
I"~
,~Jttl
.
~;
':
~. I~fit,...,.)
iti",
I -
..
':
'
" ~
~ ~ D
Fig. 37. A a-Alectoronic acid, GE. Bar 100 11m. B a-Alectoronic acid with a-collatolic acid [from Cetrelia chicitae
(W.Culb.) W. Culb. et C. Culb., GE. Bar 100 11m. C Colensoic acid, GE. Bar 100 11m. D a-Collatolic acid, GE. Bar 100 11m
A
_ _~ JJ.
.~
-, ,
,- ~
)
- ~
, .
4
I '.
f
~,
~
,
I . ."
o
'.
C
Fig. 38. A Constictic acid, An. Bar 100 flm. B Diploicin, GE. Bar 100 flm. C Fumarprotocetraric acid, GE. Bar 100 flm. D
Fumarprotocetraric acid, An. Bar 100 flm
A~
,. B
Fig. 39. A Grayanic acid (from Cladonia grayi Merr. ex Sandst.), GE. Bar lOOl1m. B Hypoprotocetraric acid, GE. Bar
lOOl1m. C Hypoprotocetraric acid, Py. Bar 100 11m. D Hypoprotocetraric acid, Q. Bar 10 11m
I
o
Fig.40. A Lobaric acid, GE. Bar 100 )..tm. B Loxodin, GA W. Bar 10 )..tm. C 4-0-Methylphysodic acid (from Parmeiia livida
Tay!.), GE. Bar 100 )..tm. D 4-0-Methylphysodic acid, GE. Bar 10 J.lm
Fig. 41. A Norlobaridone (from Parmelia subtinctoria Zahlbr.), GA W. Bar 100 flm. B Norlobaridone, GE. Bar 10 flm. C
Norstictic acid, KOH (5%); K2 C0 3 (20%) = 1; 1 (in H20). Bar 100 flm. D Norstictic acid, oT. Bar 100 flm
~ ,
,..,..
/ , /I
I I
/
!
I c \
'"
I
0
Fig.42. A Norstictic acid, Q. Bar 10 /lm. B Norstictic acid, An. Bar 10 /lm. C Pannarin, GE. Bar 100 /lm. D Psoromic acid,
GE. Bar 100/lm
.1; .'
.~ '9
j.. ".
,...

--
I
1
\.,. r
r
C
Fig. 43. A Psoromic acid, oT. Bar 100 )lm. B Psoromic acid, Py. Bar 100 )lm. C Protocetraric acid, GE. Bar 10 )lm. D
Protocetraric acid, oT. Bar lO)lm
, .
. ..

l'
--
./
.C::. .,,If.
~ /
/~ \
...
/i I
"i
'f -t
Fig. 44. A Physodic acid, GE. Bar 100 11m. B Physodic acid, GE. Bar 10 11m. C Physodalic acid [from Hypogymnia physodes
(L.) Ny!.], GE. Bar 100 11m. D Physodalic acid, GE. Bar 100 11m
\. /
I
o
I
Fig.45. A Physodalic acid, GE. Bar 10 11m. B Physodalic acid, oT. Bar 100 11m. C Salazinic acid, KOH (5%): K,C0 3 (20%)
= 1: 1 (in H20). Bar 100 11m. D Salazinic acid, oT. Bar 10 11m
A
I
Fig.46. A Salazinic acid, An. Bar 10 11m. B Stictic acid, oT. Bar 100 11m. C Stictic acid, An. Bar 10 11m. D Virensic acid, GE.
Bar 10 11m
A
I
B
..
c
Fig.47. A Virensic acid, An. Bar 10 ).Lm. B Virensic acid, oT. Bar 10 J..lm. C Picrolichenic acid, GE. Bar 100 ).Lm. D Didymic
acid, GE. Bar 100 J..lm
Fig.48. A Didymic acid, GE. Bar 10 /lm. B Isousnic acid, GE. Bar 100 ).tm. C Isousnic acid, An. Bar 100 /lm. D Placodiolic
acid, GE. Bar 100 /lm
..
./
..
., ...

A :'
Fig. 49. A Porphyrilic acid (from Stereocaulon pendulum Asah.), GE. Bar 100 [Lm. B Porphyrilic acid, GE. Bar 10 [Lm.
C Schizopeltic acid, GE. Bar 100 [Lm. D Strepsilin, GE. Bar 10 ~lm
'.
c
Fig. SO. A Usnic acid, GE. Bar 100 !lm. B Usnic acid, An. Bar 100 !lm. C Galapagin, GE. Bar 100 !lm. D Galapagin, GE. Bar
100 !lm
Fig.51. A Galapagin, An. Bar 100 J..lm. B Lepraric acid, GE. Bar 100 J..lm. C Lobodirin, GE. Bar 100 J..lm. D Roccellin, GE. Bar
100J..lm
..
c D
Fig. 52. A Roccellin, GE. Bar 10 !lID. B Sordidone, GE. Bar 10 !lID. C Sordidone, oT. Bar 100 !lID. D Sordidone, An. Bar
100!lm
c / o
Fig. 53. A Lichexanthone, GE. Bar lOOl1m. B Thiophanic acid, GE. Bar 100 11m. C Thiophanic acid, An. Bar 100 11m.
D Thuringione, GE. 100 11m
Fig. 54. A Thuringione, An. Bar 100flm. B (-)-ent-Kauran-16<x-ol, GE. Bar lOOflm. C (-)-ent-Kauran-16<x-ol, An. Bar
100 flm. D 7~-Acetoxy-hopan-22-ol, GE. Bar 100 flm
.-
~
0
6
=, c Q
~

0=-
J

0
"
A~ B
I.' ~
Fig. 55. A 7~-Acetoxy-hopan-22-ol, An. Bar lOOllm. B Hopan-15O:, 22-diol, GE. Bar lOOllm. C Hopan-15O:, 22-diol, GE.
Bar lOllm. D Hopan-15O:, 22-diol, An. Bar lOllm
Fig.56. A Friedelin, GE. Bar 100 J.1m. B Leucotylin, GE. Bar 100 J.1m. C Leucotylin, An. Bar 100 J.1m. D Retigeric acid A, GE.
Bar 10J.1m
I.
' .)
c
Fig.57. A Retigeric acid B, GE. Bar 10 J.tm. B Ursolic acid, GE. Bar 10 f..lm. C Ursolic acid, Q. Bar 100 f..lm. D Zeorin, An. Bar
lOf..lm
o L.
1! ,
,..
o
Fig. 58. A Bellidiflorin, An. Bar 10 ).tm. B Materia rubra [an unidentified compound from Usnea baileyi (Stirt.) Zahlbr.],
GE. Bar 100 ).tm. C Dissectic acid with atranorin, An. Bar 10 ).tm. Dissectic acid is an unidentified PD+ Substance from
Heterodermia dissecta (Kurok.) Awas. D a-Acetylsalazinic acid, oT. Bar lO).tm
Fig. 59. A a:-Acetylsalazinic acid, An. Bar 10 f.lm. B Placodiolic acid, GE. Bar 100 f.lm. C Placodiolic acid, An. Bar 100 f.lm.
D Bourgeanic acid, GE. Bar 100 f.lm
o
(;)
o
o c
Fig. 60. A Bourgeanic acid, GE. Bar 10 11m. B Bourgeanic acid, An. Bar 100 11m. C Acetylportentol, GE. Bar 10011m. D
Acetylportentol, An. Bar 100 11m
Fig. 61. A (-)-2-Methylene-3(R)-carboxy-18(R)-hydroxynonadecanoic acid, GE. Bar 100 )lm. B (-)-2-methylene-3(R)-

carboxy-18(R)-hydroxynonadecanoic acid, Q. Bar 100 ,Llm. C Neodihydromurolic acid, GE. Bar 100 IJ-m. D Nephrosteranic
acid, GE. Bar 100 IJ-m
Fig.62. A Nephrosteranic acid, GE. Bar 10 flm. B 2-0-Methylconfluentic acid, GE. Bar 100 flm. C 2-0-Methylconfluentic
acid, GE. Bar lOflm. D 3,5-Dichloro-2'-O-methylanziaic acid, GE. Bar lOflm
I
A
Fig.63. A 3,5-Dichloro-2' -O-methylanziaic acid, An. Bar 10 .um. B 3,5-Dichloro-2'-O-methylanziaic acid, Py. Bar 100 11m.
C Gangaleoidin, GE. Bar 100 11m. D Gangaleoidin, GE. Bar 10 11m
----~-~71
<'.
Fig.64. A Gangaleoidin, Py. Bar 100 J..lm. B 3-Hydroxycolensoic acid, Py. Bar 100 J..lm. C 3-Hydroxycolensoic acid, Py. Bar
10J..lm. D 3-Hydroxycolensoic acid, GE. Bar lOJ..lm
Fig.65. A Ergosterol, GE. Bar 100 11m. B Ergosterol, An. Bar 100 11m. C ~-Sitosterol, An. Bar 10 11m. D ~-Sito sterol, Q. Bar
100 11m
/ , I.
Fig. 66. A Evernin, GE. Bar 100~m. B Pseudoplacodiolic acid, GE. Bar 10).lm. C Pseudoplacodiolic acid, GE. Bar lO~lm.
D Pseudoplacodiolic acid, An. Bar 100 ~m
Fig. 67. A 3-Methoxycolensoic acid, GE. Bar 10 !lm. B 3-Methoxycolensoic acid, Q. Bar 10 .um. C Arthothelin, GE. Bar
100 !lm. D 2,4-Dichlorolichexanthone, GE. Bar 100!lm
chromatography because they are not suffi- in the field of lichen substances was described
ciently volatile or are too instable at elevated by C.F. Culberson (l972a). Nourish and Oliver
temperature. A further advantage of the method (1976) studied the chemotaxonomy of the
is its high speed. The first application of HPLC Cladonia chlorophaea-pyxidata complex and
2.13 Gas Liquid Chromatography 107
some allied species in Britain by HPLC. Later, nol ~ 100% methanol, 30-78 min: 100% metha-
C.F. Culberson and W.L. Culberson (1978), and nol. Reference compounds were benzoic acid
C.F. Culberson and Ahmadjian (1980) studied and solorinic acid, and the Rr values were calcu-
the extracts of Oropogon loxensis, Cetrelia lated as
cetrarioides, C. monachorum, Ramalina
sayreana and other lichens by means of HPLC. R = Rt of the peak - Rt of benzoic acid = 100
Strack et al. (1979) described the quantitative j Rt of solorinic acid '
determination of 13 aromatic lichen substances
on Li Chrosorb RP-8 using a water-methanol with Rt as retention times.
gradient. Stephenson and Rundel (1979) sepa- Kurokawa and Yoshimura (1993) identified
rated atranorin and vulpinic acid on a Micro some C]-depsides by HPLC and Yoshimura
Pak SI 10 Silica gel column with n hexane: iso- et al. (1994) determined the HPLC Rt values of
propanol: acetic acid = 100: 6 : 1 as carrier sol- numerous lichen substances on a Fine-pack
vent. Archer (1981) determined the quantitative SIL C 18 S column with the solvent system
distribution of fumarprotocetraric, crypto- MeOH:H 20:H 3P0 4 = 80:20:0.9. Huneck et al.
chlorophaeic, psoromic, merochlorophaeic, and (1994a) analyzed aliphatic lichen acids (as
4-0-methylcryptochlorophaeic acids in Austra- phenacyl-, p-nitrophenyl- or benzyl-esters) by
lian Cladonia species by HPLC. Huovinen et al. HPLC.
(1982, 1985) and Huovinen (1986, 1987) de- As in all fields of modern science, computers
scribed a standardized HPLC method for the are important tools. Mietzsch et al. (1992) devel-
analysis of metabolites from the genera Cladina oped the program WINTABOLITES for the
and Cladonia and other aromatic compounds. rapid identification of lichen substances. It
Geyer (1985) analyzed the metabolites of makes use ofHPLC Rj values, TLC-RF values, the
numerous lichen species from different colour of the TLC spots under visible and UV
genera. Schulz and Albroscheit (1989) made a light, and the lichen spot tests, and includes
HPLC analysis of orcinol, orsellinic acid, about 550 lichen substances. The program is
orcinolmonomethyl ether, evermmc acid, designed for an IBM-compatible computer and
methyl ~-orcinol-carboxylate, 3,5-dimetho- is distributed by Dr. H.T. Lumbsch (Universitat
xytoluene, methyl evernate, evernic acid, usnic Essen, Fachbereich 9/Botanik, Postfach 103764,
acid and atranorin. The lichen substances of D-45141 Essen, BRD, Germany) for the price of
three Lasallia species were identified by HPLC US $149.
by Posner et al. (1990). Lochmiiller et al. (1983)
applied a microbore, reversed-phase column 2.13
for the separation of atranorin, chloroatran- Gas Liquid Chromatography (GLC)
orin, loxodellic, glomellif~ric, 4-0-demethy-
limbricaric, divaricatic, anziaic, imbricaric, Gas liquid chromatography (GLC) has found
perlatolic, physodic, alectoronic and 4-0- only limited application in lichen chemistry be-
methylphysodic acids. Finally, Feige et al. (1993) cause most lichen substances are very polar and
published a standardized method for the identi- have low volatility. To overcome this problem,
fication of about 300 lichen substances. They more vQlatile derivatives are used. Nishikawa et
used a Spherisorb 50DS2 column (Kontron), al. (1973) analyzed the low molecular weight
5 ~m, 4 x 250 mm and the following program: 0- carbohydrates of eight lichen species as their
14min: water containing 1% ortho-phosphoric acetyl, trifiuoroacetyl and trimethylsilyl deriva-
acid ~ 70% methanol, 14-30min: 70% metha- tives by GLC under the following conditions: H2,
FID, 50 mlNzfmin; acetyl derivatives: 1.5% SE- Trifluoroacetylation: by reaction of 1 mg of the

30 on chromosorb W, 60-80 mesh, 200 x 0.4 cm sample with 0.1 ml N,N-dimethylformamide
column, temp. progr; trifluoroacetyl derivatives: and 0.2 ml trifluoroacetic anhydride at room
1% XF-ll05 on Chromosorb W; trimethylsilyl temperature for 10 min and direct injection.
derivatives: 1.5% OV -17 on Shimalite. The rela- Trimethylsilylation: 10 mg of the compound was
tive retention times of the derivatives are given treated in a small stoppered vial with 1 ml of
in Table 16. anhydrous pyridine (dried with KOH pellets),
Acetylation: by reaction of 2 mg of the 0.2 hexamethyldisilazane and 0.1 ml trim-
sample with 1ml of acetic anhydride and 1 ml ethylchlorosilane. The mixture was shaken vig-
of pyridine at room temperature for 12h. orously for about 1 min and then kept at room
Table 16. Relative retention times of the acetyl, triftuoroacetyl and trimethylsilyl
derivates of some low molecular weight carbohydrates from lichens
Carbohydrate Relative retention times of the
Acetyl deriv. Triftuoroacetyl deriv. Trimethylsilyl deriv.
Mannitol 1.00 (9.8 min) 1.00 (4.8 min) 1.00 (8.6min)

Erythritol 0.21 0.26 0.24
Arabitol 0.51 0.65 0.46
Ribitol 0.48 0.53 0.46
Fructose 0.82 0.72 0.67, 1.04
Glucose 0.85 0.72, 1.24 1.78
Sucrose 2.54 5.09 3.91
Trehalose 2.60 5.50 4.00
Umbilicin 2.42 4.51 3.69
Table 17. Relative retention times of the acetates of sterols from Pseudevernia
furfuracea
Sterol (Acetate) Relative retention time (min)

(5 a-cholestan-3~-ol = 1.00)
Cholest -5-en -3~-ol 1.36

24-Methylcholesta-5,22-dien-3~-ol 1.53
24-Methylcholesta-5,8,22-trien -3~-ol 1.60
24-Methylcholesta-5, 7,22- trie~ -3~-ol 1.68
24-Methylcholest-5-en-3~-ol 1.72
24-Methylcholestan -3 ~-ol 1.76
24-Ethylcholesta-5,22-dien-3~-ol 1.82
24-Methylcholest -7 -en-3~-ol 2.02
24-Methylcholesta -7 ,24( 28) -dien - 3~-ol 2.07
24-Ethylcholest-5-en -3~-ol 2.09
24-Ethylcholestan- 3~-ol 2.15
24-Ethylcholest-7 -en-3~-ol 2.46
Column: 3% SE-30, temp. 270C
2.16 Derivatization lO9
temperature for 5 min. From 0.1 to 0.5 J..Ll of the thylated to derivatives which are useful for their
resulting reaction mixture were used for injec- identification.
tion into the gas chromatograph. Phenacyl esters of aliphatic acids are suitable
Gaskell et al. (1973) analyzed the hydrocar- derivatives for their HPLC analysis (Huneck et
bons from three lichens by GLC and Furuya et al. 1994a).
al. (1966) some lichen anthraquinones. Ikekawa Secondary aliphatic alcohols can be easily
et al. (1965) reported on the GLC of zeorin and oxidized to the corresponding ketones by Jones'
other triterpenes. Zeorin has a retention time of reagent.
4.96min (1.5% SE-30 on Gas Chrom P, 80-
100 mesh, 150 x 4mm, 225C, 80mlNzlmin). 1. Acetylation of a phenol or an alcohol with
Shibata et al. (1965) found that free zeorin gave acetic anhydride-pyridine.
two peaks, the minor one corresponding to The compound (0.1 g) is dissolved in dry
zeorinine. The relative retention times for the pyridine (2-5 ml) and acetic anhydride
acetates of the sterols isolated from Pseud- (Ac 20, 2ml) added. After 24h at room tem-
evernia furfuracea are summarized in Table 17 perature, the mixture is diluted with water
(Wojciechowski et al. 1973). (30 ml), the precipitate removed by fil-
tration, washed with water, dried at room
2.14 temperature and recrystallized from chlo-
X-Ray Analysis roform-methanol.
2. Acetylation with acetic anhydride-sul-
X-Ray analysis is the only physical method phuric acid.
which gives directly the complete structure, ste- The compound (0.1 g) is shaken (or mag-
reochemistry and absolute configuration and netically stirred) with a mixture of acetic
has been applied in lichen chemistry for numer- anhydride (5 ml) and conc. sulphuric acid
ous compounds: Table 18. (1 drop) till the compound has dissolved.
X-Ray analysis needs only a small crystal of After 24h at room temperature, the reaction
about 0.2-1 mm in length of the corresponding mixture is worked up as under (1). Aro-
compound. Concerning the method see, e.g. matic aldehydes react under these condi-
Keller (1982). tions to diacetates.
3. Methylation of carboxylic and phenolic hy-
2.15 droxyl groups with diazomethane.
Laser Microprobe Mass Spectrometry Preparation of an ethereal solution of
(LAMMA) diazomethane. Caution! Diazomethane is
extremely toxic and explosive, and all op-
By this method, the lichen substances are erations should be conducted in a well-
ionized by laser light and analyzed in a mass ventilated hood behind a safety screen.
spectrometer: Mathey (1981), Mathey et al. a) From N-nitrosomethylurea. To a mixture of
(1987).
KOH in H20 (50ml, 50%) and diethyl ether
(100ml) in an Erlenmeyer flask (300ml) is
2.16 added N-nitrosomethylurea (5 g) in small
Derivatization portions at OC (ice bath) under rotating
the flask. After 15 min, the yellow ethereal
Many lichen substances have hydroxyl and (or) solution of diazomethane is' decanted and
carboxyl groups which can be acetylated or me-
Table 18. X-Ray analysis of lichen substances
Lichen substance Literature
Acetyldihydro-p-bromobenzoylportentol Ferguson and Mackey (1970)

(+ )-Aspicilin Quinkert et al. (1985)
Atranorin Brassy et aI. (1982)
16~- Bromobenzoyl-6-ketoleucotylin Nakanishi et al. (1968);
Yosioka et aI. (1969a)
6a- Bromobenzoylzeorin Nakanishi et al. (1971)
4-Bromonephroarctin Nuno et al. 1969
3~, 12 ~- Di-p-bromo benzoylpyxinol Yamauchi et al. (1969)
(+)-Dibromodehydrotetrahydrorugulosin Kobayashi et al. (1968, 1970)
Eriodermin Connolly et aI. (1984b)
Graciliformin Alagna et al. (1990)
Graphenone Miyagawa et al. (1994)
Graphisquinone Miyagawa et aI. (1994)
22 a-Hydroxy-3,4-secostictan-3-oic acid Corbett et al. (1982)
Hypostrepsilic acid Miyagawa et al. (1993)
Iodoacetylvicanicin Dyer et al. (1967)
Lepranthin Polbom et al. (1995)
Methyl isorhizonate Blaser et aI. (1992)
4-0-Methylcryptochlorophaeic acid Shibuya et aI. (1983)
Pentaacetylnorstictic acid Gohrt (unpubl. data)
Phlebic acid D Bachelor et al. (1990)
(-)-Placodiolic acid Connolly et al. (1984a)
(-)-Pseudoplacodiolic acid Huneck et al. (1981)
Rearranged product of Yang et aI. (1973)
2,4',9' -tribromoeumitrin B
Retigeranic acids A and B Sugawara et aI. (1991)
Retigeranic acid A p-bromoanilide Kaneda et aI. (1974)
Roccellaric acid Mulzer et al. (1993)
Secalonic acid A Howard et aI. (1976)
Sekikaic acid Kinoshita et al. (1993)
Solorinine Matsubara et al. (1994)
Stictane-3~,22a-diol Corbett et al. (1982)
Tetraacetylsimonyellin Elix et al. (1995)
Thiomelin Elix et al. (1987d)
Tri-O-acetylchodatin lix et al. (1994a)
Triacetylleprolomin lix et al. (1978a)
Triacetylrhodocladonic acid McLean et al. (1983)
(-)-Usnic acid Norrestam et al. (1974)
Usnic acid Behrens et aI. (1976)
(+)-Usnic acid a-phenylethylimine Huneck et aI. (1981)
(+)-Usnic acid sodium salt 2+ hydrate Ribar et al. (1993)
Wrightiin Maass and Hanson (1986)
dried with some pellets of KOH at Oc, b) From N-methyl-N-nitrosotoluene-p-

Diazomethane decomposes slowly and can sulphonamide. Ethanol (95%, 50 ml) is
be stored at OC in a flask with a cork stop- added to a solution of KOH (lOg) in H2 0
per for some hours only. (15ml) in a round bottomed flask (250ml)
2.16 Derivatization 111
equipped with a dropping funnel and a con- To a solution of the phenol (30 mmol) in
denser for distillation. The condenser is dimethylformamide (fourfold amount in
connected to an Erlenmeyer flask contain- weight) are added anhydrous potassium
ing diethyl ether (40ml). The inlet tube of carbonate (90mmol) and dimethyl sulphate
the receiver is below the surface of the ether, (60 mmol) and the mixture is heated on the
and the receiver is cooled to OC in an ice steam bath for 15 min. For every additional
bath. The flask containing the solution of OH-group this procedure must be repeated.
KOH is heated in a water bath to 60-65C After finishing, the reaction water is ad-
and a solution of Diazald (N-methyl-N- ded, the precipitate removed by filtration,
nitrosotoluene-p-sulphonamide, 42 g) in washed with hydrochloric acid (10%) and
Et2 0 (250 ml) is added through the drop- water, dried at room temperature and re-
ping funnel over a period of 45 min. The crystallized from a suitable solvent.
rate of distillation should be equal to the 5. Methylation of phenolic hydroxyl groups
rate of addition of Et20. After the addition with methyl iodide and potassium carbon-
of the ethereal solution of Diazald, further ate in acetone.
Et 2 0 (40 ml) is added slowly through the The phenol (0.1 g) is heated with methyl
dropping funnel, and the distillation is con- iodide (10 ml) and anhydrous potassium
tinued until the distilling Et2 0 is colourless. carbonate (10g) in anhydrous acetone (50-
The compound (0.1 g) is dissolved in di- 100ml) on a steam bath for 12-18h, the in-
ethyl ether (10-20ml), acetone (10ml) or a organic material removed by filtration,
mixture of diethyl ether: methanol = 8: 2 the solvent removed i.vac. and the residue
(10 ml) and at OC an ice-cold solution of recrystallized.
diazomethane in diethyl ether is added 6. Phenacyl esters of acids.
dropwise until the yellow colour persists. The acid (0.3 g) is neutralized with the
The solvent and excessive diazo methane are equivalent amount ofKOH in methanol and
removed i.vac. and the residue is crystal- the solvent removed i.vac. To the residue
lized from methanol. benzene (10 ml) is added and removed i.vac.
In carboxylic acids with additional phe- After the addition of the equivalent amount
nolic hydroxyl groups the carboxyl groups of phenacyl bromide and 16-crown-8 (5 mg)
are more acid than the phenolic groups and the mixture is heated under reflux in
can be specifically methylated by a very acetonitrile (10 ml) for 1 h. After usual work
short treatment (5 to lOs) with diazo me- up, the crude phenacyl ester is either crys-
thane at OC. Some phenolic groups are dif- tallized from n-hexane or purified by
ficult to methylate and need reaction times chromatography.
up to 24h at room temperature. 7. Benzyl esters of acids.
A solution of the acid (1 mmol) in anhy-
4. Methylation of phenolic hydroxyl groups drous dimethylformamide (8ml) and an-
with dimethyl sulphate and potassium car- hydrous potassium hydrogen carbonate
bonate in dimethylformamide. (KHC0 3, 1.1 g) are stirred at room tempera-
Caution! Dimethyl sulphate is also a very tur~ while benzyl bromide (1.2mmol) is
toxic compound and the oily liquid should added dropwise. The reaction mixture is
never be brought in contact with the skin. stirred at room temperature for 20 hand
Dimethyl sulphate should be handled only then boiled under reflux for 2h. The cooled
under a hood. reaction mixture is diluted with Et2 0, the
solution dried with NaZS0 4, filtered, the sol- The conditions for the corresponding reactions
vent removed i.vac. and the residue purified are:
by chromatography.
8. Benzyl ethers of phenolic compounds. 1. The depside (0.1 g) is dissolved by stirring
The phenol (l mmol), benzyl bromide with a glass rod in conc. sulphuric acid (5 ml)
(1.2mmol) and anhydrous potassium car- at Oc. The clear solution is poured on
bonate (K ZC0 3, 0.5 mmol) are heated under crushed ice (30g) after 10-15min, the reac-
reflux in anhydrous acetone (lOOml) for tion mixture extracted with EtzO (3 X 10 ml),
20 h. The reaction mixture is worked up as the ethereal solution washed with brine
described under (7). (3 ml), dried with NaZS0 4 and the EtzO re-
9. Hydrogenolysis of benzyl esters and benzyl moved i.vae. The resulting mixture of the
ethers. cleavage products is analyzed by TLC and
A solution of the benzyl ester or the benzyl separated by column chromatography, pre-
ether (l mmol) in ethyl acetate (lOOmI) con- parative TLC or by fractional crystallization.

taining 10% palladium on charcoal (0.1 g)
is shaken or magnetically stirred in an at-
mosphere of hydrogen for 20h. The cata-
lyst is removed by filtration, the solvent HO
R
5
eo-o ' o / 0 H H20
OH
A --
eOOH HO
tbc R
5
eOOH H0o/0H
OH
+ A
CO
evaporated and the residue purified by o
R' R' H
chromatography.
10. Oxidation of a secondary hydroxyl group to 2. The depside is boiled with a 5% solution of
a ketone. KOH or NaOH in H20 for 30-60min.
The alcohol (0.1 g) is dissolved in acetone Depsides with a free hydroxyl group in p-
(5-20ml) and Jones' reagent [solution of position to the ester bond yield the corre-
chromium trioxide (26.7 g) and cone. sponding phenols:
sulphuric acid (23ml) in water (100ml)]
R R
added dropwise at room temperature until
a brown colour of the reaction mixture per-
sists (3-10 min). A solution of oxalic acid HO
~ eO-o%H
5
OH
A
H20
-
eOOH HO
~
5 +
OH
H0'o/0H
A -2eo
2
in water (l0%) is added, the precipitate R' R'
collected, washed with water, dried and 3. Boiling of a depside with methanolic KO,H or
recrystallized. NaOH (5%) under a hydrogen atmosphere
(to avoid oxidation of the phenols) for 0.5-
2.17 2 h give the methyl ester of the S part and the
Cleavage of Deps~des phenol A:
The ester bond of depsides can be cleaved by R R

hydrolysis with eO-0'%H ME'OH &eoOMe- H0'o/0H
& 5 A --5 + A
MeO OH CO MeO OH co
1. cone. sulphuric acid, R' ~ R' ~
2. potassium or sodium hydroxide,
3. methanolic potassium or sodium hydroxide, 4. Prolonged boiling (5-20h) of a depside with
or by an alcohol (100%) yields the corresponding
4. alcoholysis with methanol or tert-butanol. ester of the S part and the phenolic part (A).
Melting Points of Lichen Substances 113
Table 19. Melting points oflichen substances
Melting point (0C) Compound Melting point (OC) Compound
1,8-Cineol 96 Nephrosterinic acid

5 ~-Fenchol 97-100 3-0-~- D-Glucopyranosyl-D-
16 Caprylic acid mannitol
22 n-Heptadecane 98-99 19-Acetoxylichesterinic acid
26.5-27.5 Acetyl-a-tocopherol 100-102 Micareic acid
35-38 4-Dechloro-8-0- 102 Ribitol
methylthiomelin 102-103 Arabitol
38-40 a-Terpineol 102-103 Protoconstipatic acid
40-41 Methyl protolichesterinate 102-104 Brialmontin 1
40-46 Olivetol 103 Isohyperlatolic acid
41-42 Ethyl divaricatinate 103-105 Fructose
48 a-Fenchol 103-107 Lactone carboxylic acid from
51 Camphene Lecanora rupicola
51 Divarinol 104-105 Patagonic acid
53 Manool 104-105 Rangiformic acid
53 Pentadecanoic acid 105-107 Dihydropertusaric acid
55 Rimuene 105-107 ---7 136-137 2,2'-Di-O-methylanziaic acid
60 1,1-Dimethylnoneicosyl 105-107.5 Isohyperpicrolichenic acid
everninate 106-108 ~-Collatolic acid
63 Orcinolmonomethylether 106-108 Orcinol
63-64 Palmitic acid 106-109 Brialmontin 2
69.4 Stearic acid 107 allo-Protolichesterinic acid
70-72 Hierridin 107.5 Protolichesterinic acid
71-72 2-0-Methylsuperlatolic acid 107-108 Perlatolic acid
73-74 Ethyl everninate 107-109 Dimethylsulfone
80.5-80.6 Fukinanolide A 108 Superplanaic acid
82-83 2-0-Methylhyperlatolic acid 108-109 Constipatic acid
83-84 (-)-2-Methylen-3(R)- 108-109 Isomuronic acid
carboxy-18(R)- 108-110 Superpicrolichenic acid
hydroxynonadecanoic acid 108-111 Methyl 4-0-
83-84 n -Nonacosan -10-01 demethylbarbatate
83-85 Isorangiformic acid 109-127 2' -O-Methylstenosporic acid
84 ()-Lichesterylic acid 110 ---7160-162 Divaronic acid
84 2-0-Methylisohyperlatolic 110-111 Murolic acid
acid 110-111 Planaic acid
85-87 2-0-Methylnorsuperlatolic 110-111 Roccellaric acid
acid 111-112 Neuropogolic acid
90-95 a-Collatolic acid hydrate 111-113 2-0-Methylnorstenosporic
93-94 Muronic acid acid
93-94 Prasinic acid 111-115 Cholesta-3,5-dien -7 -one
94-95 2-0-Methylperlatolic acid 112-113 Stenosporic acid
94-96 19-Acetoxyprotolichesterinic 112-114 Evernin
acid 113 Ethyl haematommate
94-99 1-( O-a-D-Glucopyranosyl)- 113 Hyperlatolic acid
2(S),25(R)-hexacosanediol 114-115 Lichesterol
95 Nephrosteranic acid 114-115 2'-0-Methylsuperlatolic acid
95-96.5 Stigmast -4-en -3-one 114-116 3-Acetoxy-3,4-secostict-
95-97 Hyperpicrolichenic acid 4(23)-en-22a-ol
Table 19. Continued
Melting point (0C) Compound Melting point (OC) Compound
114-122 Norrangiformic acid 127-129 2' -0-Meythylanziaic acid

115-120 Norlobariolmethyl 127.5-128.5 Ergosta-7, 24(28) -dien -3~-ol
pseudoester 128 3-Chloroperlatolic acid
116 Microphyllinic acid 128 Hyperplanaic acid
116-117 Megapicrolichenic acid 128-130 3-Chloroimbricaric acid
116-117 2-0-Methylanziaic acid 128-130 4-0" Demethylsquamatic acid
117-118 ~-Collatolic acid 129-130 Contortin
1l7-118 Stigmasta -3,5-dien-7 -one 129-131 2,2'-Di-0-methyldivaricatic
118-121 ~-Orcinolmonomethylether acid
119-120 Oxostenosporic acid 130 Roccellic acid
120 Subsphaeric acid 130-132 Acarenoic acid
120-121 a-Alectoronic acid hydrate 131 Episterol
120-122 3-Methoxycolensoic acid 131-132 Ethyl orsellinate
121-126 Cholestan-3~-ol 132-133 Nostoclide II
121.5 meso-Erythritol 132-133.5 Caperatic acid
122 Benzoic acid 132-133.5 Loxodin
122-123 Isohyperplanaic acid 132-133.5 2-0-Methyltenuiorin
122-123 Neodihydromurolic acid 132-134 2,4-Di-O-methylnorsekikaic
122-123 Siphulitol acid
122-124 4-0-Demethylplanaic acid 132-145 24~-Ethylcholestan-3~-ol
123 4-0-Methylolivetolcarboxylic 133-137 Homosekikaic acid
acid 134.5 Boninic acid
123-124 Lichesterinic acid 134-135 Tagatose
123-124 Protopraesorediosic acid 134-136 Methoxymicareic acid
124 Anziaic acid 135 2,2' -Di-O-methylstenosporic
124 Atranol acid
124 Methyl 4-0- 135-136 Epanorin
methyleriodermate 135-136 2-0-Methylconfluentic acid
124 Methyl sekikate 135.5-136 meta -Scro biculin
124-125 a-Collatolic acid 135-138 Glomellic acid
124-125 2-0-Methylnorimbricaric 136 4-0-Demethylsphaerophorin
acid 136.5 Montagnetol
124-125 4-0-Methylolivetoric acid 137 Conloxodin
124-126 a-Amyrone 137 Loxodellic acid
124-126 2"-0-Methyltenuiorin 137 Nephromopsinic acid
125 Methyl 3, 4-dicarboxy-3- 137 Normiriquidic acid
hydroxy-19- 137-138 2,2'-Di-O-methylimbricaric
oxoeicosanoate acid
125-126 Bourgeanic acid 137-138 Divaricatic acid
125-126 Hyperhomosekikaic acid 137-139 2-0-Methylhiascic acid
125-126 Imbricaric acid 137-139 Norcaperatic acid
125-128 Methyl 3'-methyllecanorate 137-141 Sphaerophorin
126 2' -O-Methylimbricaric acid 138 3-Chlorostenosporic acid
126-127 2' -O-Methylperlatolic acid 138~139 ~-Alectoronic acid
126-128 Nordivaricatic acid 138-139 Methyl orsellinate
126-130 Fecosterol 138-139 4' -0-Methylpaludosic acid
127-128 Graphisquinone 138-144 Lanosterol
127-128.5 2' -O-Methylisohyperlatolic 139-140 Stenosporonic acid
acid 139-140 Umbilicin
Table 19. Continued
Melting point (0e) Compound Melting point caC) Compound
139-140.5 Chloroatranol 150-152 15 a-Acetoxy-22-

139-140.5 Praesorediosic acid hydroxyhopan-24-oic acid
140-141 Miriquidic acid 150-152 Isousnic acid
140-141 ~-Sitosterol 150-152 Leprapinic acid methyl ether
140-142 Trypethelone methyl ether 151 Oliveto ric acid
140-144 Methyl ~-orcinolcarboxylate 151-151.5 Stigmast-7 -en-3~-ol
140-145 4.2"-Di-0-methylgyrophoric 151-152 4-0-Methylphysodic acid
acid 151-153 Volemitol
140.5-141 24~-Methylergosterol 152 4-0-Demethylglomellic acid
141-142 4-0- 152 4'-0-
Methylcryptochlorophaeic Methylcryptochlorophaeic
acid acid
141-146 24~-Methylchloestan-3~-ol 152-153 Condidymic acid
141-150 Clionasterol 152-153 4-0-
142 Isosphaeric acid Methylisocryptochlorophaeic
142-143 5-Chlorodivaricatic acid acid
142-143 2'-0-Methyldivaricatic acid 152-154 Norargopsin
142-143 Methyl evernate 152-158 Campesterol
142-144 Orcinyllecanorate 153-154 Aspicilin
143-144 4,6-Dihydroxy-2-methoxy -3- 153-154 Subdivaricatic acid
methylacetophenone 154 Methyl ascomatate
143-145 Glomelliferic acid 154-155 Acaranoic acid
143-145 Neoxanthin 154-155 (dec.) 3.5-Dichloro-2' -0-
144-146 2' -O-Methyltenuiorin methylanziaic acid
144-147 24 ~-Ethylcholest-7-en-3~-ol 155-156 Poriferasterol
145 Isomegapicrolichenic acid 156 5-Chlorolichexanthone
145-149 Olivetolcarboxylic acid 156 4-0-Demethylglomelliferic
145-151 Cholesterol acid
146 4-0-Demethylloxodellic acid 156 Methyl 8-hydroxy-4-0-
146 Isomerochlorophaeic acid demethylbarbatate
146-147 Isopatagonic acid 156.4 Sativic acid
146-148 2' -O-Methylatranorin 156-157 Erythrin
146-152 Epiphorellic acid II 156-157 2-0-Methylsekikaic acid
147 (dec.) Glucose 156-157 Submerochlorophaeic acid
147-148 4,4'-Di-0- 156-158 8-Hydroxydiffractaic acid
methylcryptochlorophaeic 156-158 Placodiolic acid
acid 156.5-159 3-Methoxylividic acid
147-148 2' -0-Methylmicrophyllinic 157-158 Brassicasterol
acid 157 Confluentic acid
147-149 Methyl 6-0- 157-158 Ergost-5-en-3~-ol
methylnorascomatate 157-158 1-Hydroxy-2,4-dichloro-6,8-
148 Vulpinic acid dimethyl-7-
148-149 Melacarpic acid methoxyxanthone
148-150 Isodidymic acid 157-159 Divaric acid
148-151 Fungisterol 157-160 Arabinose
148-152 Methyl8-hydroxybarbatate 157-179 Divaric acid
149-151 Glomellonic acid 158-159 3-Chlorodivaricatic acid
149 -7 298 (dec.) Methyllecanorate 158-160 Canesolide
150-151 Sekikaic acid 158-160 Epiphorellic acid I
Table 19. Continued
Melting point (0C) Compound Melting point (0C) Compound
158-160 Lepraric acid 166 2'-0-Methylnephroarctin

158-163 ~-Orcinol 166-167 (dec.) Isonotatic acid
158.5-160 Subdidymic acid 166-167 Mannitol
158.5-17l Paludosic acid 167 Methyl 2-0-
159 3' -0-Methylevernic acid methyleriodermate
159-160 Subsekikaic acid 167-168 Phenarctin
159-161 Loxodellonic acid 167-169 (dec.) Arthoniaic acid
159-182 4' -0-Methylnorsekikaic acid 167-169 Arthonin
160 Lupeone 168 Methyl 2,2'-di-O-
160 4'-0- methyleriodermate
Methyinorcryptochlorophaeic 168-169 Isonorobtusatic acid
acid 168-169 (dec.) Pseudocyphellarin B
160-162 Isosubpicrolichenic acid 168-170 2,2'-Di-O-methyltenuiorin
160-162 2' -O-Methylphysodic acid 168-170 3-Methoxy-2,4-di-0-
160-163 Ergosterol methylgyrophoric acid
161-163 Peltigeroside 168-170 Stigmasterol
162 4-0-Demethylmicrophyllinic 168.5-169 4,5-Di-O-methylhiascic acid
acid 169 ~-Cryptoxanthin
162 2' -0-Methylevernic acid 169-173 2,4-Di-O-methylgyrophoric
162 2' -0-Methylnorbabatic acid acid
162-166 Methyl 5-chloro-4-0- 170 (dec.) Prunastric acid
demethylbarbatate l70-l71 3-Methoxyumbilicaric acid
163 Eugenitin 170-173 Buellolide
163-164.5 Sandaracopimaric acid 171 2'-0-
163-165 8', 9'-Di-O-ethylsalazinic Methylisopseudocyphellarin
acid A
163-165 Galapagin 171-172 4-0-Demethylbaeomycesic
163-165 Graphenone acid
163-165 3-Hydroxycolensoic acid 17l-172 Sa, 8a-Peroxyergosteryl
163-170 Ramalinolic acid divaricatinate
164 Methyl 5-chloronorobtusate 172 Methyl 2'-0-
164-165 6-Ethyl-6-n-pentyl- methyleriodermate
pentadecan-4,5,7,8,15- 172-173 (dec.) Haematommic acid
pentol-15-acetate 172-174 Evernic acid
164-165 Indolyl-3-acetic acid 173 Methyl barbatate
164-165 Leprapinic acid 173-174 Colensoic acid
164-165 Subpicrolichenic acid 173-175 Pseudocyphellarin A
164-166 Merochlorophaeic acid 173-176 2,4,5-Tri-O-methylhiascic
164-166 3-0-Methylpannaric acid acid
165 ~-Collatolic acid 173.5-174 Ergosta-7 ,22-dien-3~-ol
165 Methyl eriodermate 174 (dec.) Diploschistesic acid
165-166 8-Methoxytrypethelone 174 2-0-Methylobtusatic acid
methyl ether 176 4' -0-Methylnorhomosekikaic
165-167 5-0-Acetyl-4-0- acid
methylhiascic acid 176-177 (dec.) 4-0-Demethylbarbatic acid
165-170 Hyponephroarctin 176-177 Hypothallin
165-173 (dec.) Didymic acid 176-178 (dec.) 2"-0-Methylgyrophoric acid
166 Galactose 176-178 (dec.) Oxysiphulin
Table 19. Continued
Melting point (OC) Compound Melting point (0C) Compound
176-179 Alectorialic acid demethylbarbatic acid

176.5-177.5 Rhizocarpic acid 185-187 Sucrose
176.5-178 y-Carotene 185-203 (dec.) U mbilicaric acid
177 Mutatoxanthin 186-187 3-Hydroxyumbilicaric acid
177-177.5 Methyl 3,5- 186-187 Nostoclide I
dichlorolecanorate 186-189 (dec.) Grayanic acid
177-178 Acetyltylolupenol B 187-188 o:-Carotene
178 (dec.) Vittatolic acid 187 (dec.) Barbatic acid
178-180 25-Acetoxy-20(S),24(R)- 187-189 (dec.) Ergochrome AB
epoxy-dammaran-3~-ol 187-194 3-Hydroxyphysodic acid
178-180 ~-Amyrone 188 Norlobaridone
178-180 Ovoic acid 188-189 (dec.) 5-0-Methylhiascic acid
178-180 ~ 238 (dec.) Tenuiorin 188-189 Retigeranic acid B
178-180 (dec.) Crustinic acid 188-190 25-Acetoxy-20(S),24(R)-
178-194 Tetrahydroxyfatty acids epoxy-dammaran-3-one
178.5-179 Camphor 189-190 Diffractaic acid
179-180 Conorlobaridone 188-190 1,7 -Dihydroxy-2,4-dichloro-
179-182 Protosiphulin 6,8-dimethylxanthone
180-181 9-MethyI4- 188-195 Isomultiflorenone
hydroxypannarate 189 Pseudonorrangiformic acid
180-182 Pseudoplacodiolic acid 189-190 Lichexanthone
181 l' -Chloronephroarctin 190 Hop-21 0:-H-22(29)-en-3-one
181-182 Subpaludosic acid 190 2'-0-
181-184 ~-Carotene Methylpseudocyphellarin A
182 2'" -0- Ethyl-~-alectoronic 190-193 Diacetyl-12-deoxypyxinol
acid 190-193 0-0:-D-Galactopyranosyl-( 1
182-183 4' -Hydroxy-8- ~ 6)-0-~-D-galacto-
methoxytrypethelone pyranosyl-(l ~ l)-D-
methyl ether glyceritol
182-184 Cryptochlorophaeic acid 190-204 Moretenone
182-184 Dechloropannarin 190-220 Picroroccellin
183-183.5 Congrayanic acid 190.5-200 (dec.) Hiascic acid
183-184 Ergosterol-50:,80:-peroxide 191-193 2' -O-Methylnorobtusatic
183-185 1,4,5,8-Tetrahydroxy-3-ethyl- acid
naphtho-2,6-quinone 192-193 Echinenone
183-187 o:-Amyrin 192-193 Norlobariol
184 (dec.) Lecanoric acid 192-194 8-Hydroxybarbatic acid
184 ~-Ordnolcarboxylic acid 192-201 Nephroarctin
184-185 Glomelliferonic acid 193 o:-Alectoronic acid
184-186 2,4-Dichlorolichexanthone 193 Lutein
184-187 Picrolichenic acid 193-194 (dec.) 2-Dechlorothiomelin
184-192 Taraxanthin 193-194 1,8-Dihydroxy-3,6-
184-196 Haemoventosin dimethoxyxanthone
184-198 (dec.) Orsellinic acid 193-194, 4-0-Methylvicanicin
185 Lepranthin 193-196 Chrysophanol
185 (dec.) Siphulin 194-196 1-Methoxy-4-chloro-5,8-
185 Thiomelin dihydroxy-6-
185-186 (dec.) 5-Chloro-4-0- methylxanthone
Table 19. Continued
Melting point caC) Compound Melting point caC) Compound
194-200 ~-Amyrin 208 Borneol

195-196 Monoacetylfallacinol 208 Violaxanthin
195-200 Constictic acid 208-208.5 Chloroatranorin
196 (dec.) Atranorin 208-209 Fern-9( 11 )-en-3~, 12a-diol
196-197 3-0-Acetylpyxinol 208-209 (dec.) Obtusatic acid
196-197 4,4'-Dibutyrylscabrosin 208-209 (dec.) Haemophaein
196-197 Lobaric acid 209-210 Lividic acid
198 2' -0-Methylphysodone 210-212 Fern-9(11)-en-3~,12~-diol
198-198.5 7a-Acetoxyhopan-6a,22-diol 212 Elatinic acid
198-199 6-H ydroxymethyleugenitin 212-213 Northiomelin
198-201 Ergosta-5,7,14,22-tetra en -3~- 212-216 Lupeol
01 212-231 3~-Hydroxyolean-12-en-11-
198-202 Norpannarin one
198.5-199 6a-Acetoxyhopan-7a,22-diol 213 4-Acetyl-4' -
199-200 4-Chlorolichexanthone hexanoylscabrosin
199-201 Isoschizopeltic acid 213 6-0-Methylaverantin
199-201 Scensidin 213-214 16~-AcetOJ\."yhopan-6a,22-
200-201 (dec.) Alectorialin diol
200-202 3~- Acetoxyfern -9(11) -en- 214-215 Demethylleprapinic acid
19~-01 214-215 Gangaleoidin
200-203 4-0-Methylphysciosporin 215 (dec.) Decarboxythamnolic acid
200-203 Pinastric acid 215 6-0-Methylaverythrin
200-205 15a-Acetoxyhopan-22-o1 215 (dec.) 4-0-Methylgyrophoric acid
200-214 Tri -0-methylarthothelin 215-216 2a-Acetoxystictan-3~,22a-
201 (dec.) Isopseudocyphellarin A diol
201 Solorinic acid 215-216.5 Methyl virensate
201-202 Physciosporin 215-217 Pulvinic acid
202-203 Chlorogranulatin 215.5 Zeaxanthin
202-204 (dec.) Haemathamnolic acid 216-217 (-)-ent-Kauran-16a-ol
202-205 5,7-Dichlorolichexanthone 216-217 Pannarin
203 Trehalose 216-220 Eumitrin Al
203 Usnic acid 216-220 2-0-Methylsquamatic acid
203-205 2-0-Acetyltenuiorin 216.5 Wrightiin
204 (dec.) 6-0-Methylnorascomatic 216.5-217.5 4-Acetyl-4' -butyrylscabrosin
acid 217-218 Canarione
204-207 Fulgidin 218 Canthaxanthin
204.5-207 Methyl 5,1'- 218 Islandicin
dichloropsoromate 21S-220 22a-Hydroxystictan-3-one
205 (dec.) Physodic acid 21S-220 (dec.) 9-Methyl pannarate
205-206 Erythroglaucin 219 S-O-Methylthiomelin
205-210 4,5,7 -Trichlorolichexanthone 219-220 (dec.) Barbatolin
206 Antheraxanthin 219-222 Hop-21-~H-22(29)-en-3-
206-207 (dec.) Barbatolic acid one
206-207 Roccellin 220, 4-0-Methyldiploicin
206-210 Parietin 220-221 Argopsin
207-209 4-0-Demethyldiffractaic acid 220-221 Pulvinamide
207-209 2' -O-Methylhiascic acid 220-221 Ramalinaic acid
207-209 Nornotatic acid 220-222 Retig~ranic acid A
Table 19. Continued
Melting point (OC) Compound Melting point (OC) Compound
220-225 (dec.) Gyrophoric acid 230-232 3~- Acetoxyfern-9( 11 )-en-

220-240 (dec.) a-Acetylhypoconstictic acid 12~-01
221-226 6a- Acetoxyhopan-22-01 230-232 (dec.) Allorhizin
222-223 Astaxanthin 230-232, softening at 215 Methyl 5,1'-
222-223 2-Chlorolichexanthone dichloronorpsoromic acid
222-224 1,5-Dimethoxy-4-chloro-6- 230-235 (dec.) Conprotocetraric acid
methyl-8- 230-260 (dec.) Physodalic acid
hydroxyxanthone >230 (dec.) Conphysodalic acid
222-224 Pulvic acid lactone 231 Phthalic acid
223 (dec.) Thamnolic acid 231-232 2a,3 ~- Diacetoxystictan- 22a-
223-224 Acetylportentol 01
223-225 (dec.) Subnotatic acid 232 6a, 16~-Diacetoxyhopan-22-
224-225 (dec.) Baeomycesic acid 01
224-225 2-Dechloro-8-0- 232 Diploicin
methylthiomelin 232-233 Leoidin
224-226 Fulgoicin 232-235 4-Chloro-6-0-
224-226 Hopan-6a,7~,22-triol methylnorlichexanthone
224-243 4-Dechlorothiomelin 233-234 Averantin
224-288 Methyl gyrophorate 233-234 (dec.) Schizopeltic acid
225 6a- Acetoxyhopan-16~,22- 233-247 4,7-Dichloro-3-0-
diol methylnorlichexanthone
225 myo-Inositol 233.5 Phyllopsorin
225-226 (dec.) Notatic acid 234 Chlorolecideoidin
225-226 Pyxinol 234-235 30-Nor-21a-H-hopan-22-one
225-227 (dec.) Hypothamnolic acid 234-236 Eriodermin
225-227 2,4,5-Trichlorolichexanthone 234-236 8-0-Methylfragilin
226-227.5 3-0-Demethylscensidin 235-236 20a-Acetoxyhopan-6a,22-
226-228 Allantoin diol
226-228 3-Dechlorogangaleoidin 235-237 22a- Hydroxy-3,4-secostict-
226-228 IS-Methyl pannarate 4(23)-en-3-oic acid
227 3~-Acetoxystictan-2a,22a- 235-237 Loxodinol
diol 235-240 (dec.) Convirensic acid
227-229 Norascomatic acid 235-240 (dec.) Norcolensoic acid
228 16 ~- Acetoxyhopan -22-01 235-240 Phlebic acid D
228-229 Chlorophyllopsorin 236-242 Zeorin
228-229 (dec.) 4-0- 237-240 (dec.) Consuccinprotocetraric acid
Methylhypoprotocetraric 238 3'-Dechlorolecideoidin
acid, 238-239 Leprolomin
228-229 (dec.) Squamatic acid 238-239 Taraxer-14-en
228-229 2,4,7- 238-240 Eumitrin B
Trichloronorlichexanthone 238-240 Hypophysciosporin
229 Hopan-7~,22-diol 240 (dec.) Cetraric acid
229-231 (dec.) Averythrin >240 (dec.) Siphulellic acid
230 Hypopsoromic acid 240-241 Diacetylpyxinol
>230 (dec.) a-Acetylconstictic acid 240-242 (dec.) Succinprotocetraric acid
230-231 Hopan-6a,7a,22-triol 240-242 Taraxerone
230-231.5 3-Dechloro-4-0- 240-245 (dec.) Confumarprotocetraric acid
methyldiploicin >240 (dec.) Sodium usn~ate
Table 19. Continued
242 Ascomatic acid 254-255 Pyxinic acid

242-243 (dec.) Hypoprotocetraric acid 254-256 (dec.) 2,4,7-
242-243 Norgangaleoidin Trichloronorlichexanthone
242-243 Thiophanic acid 254-260 Emodin
242-244 Cryptostictic acid 255-255.5 Methyl 3-0-acetylpyxinate
243-244 3p-Acetoxystictan-22a-ol 255-257 4,5-Dichloro-3-0-
243-245 Pannaric acid methylnorlichexanthone
243-245 Phlebic acid A 255-257 2,5-Dichloro-6-0-
244-246 Fallacinol methylnorlichexanthone
244-246 2,4,5-Trichloro-3,6-di-0- 255-257 8-0-Methylpannaric acid
acetylnorlichexanthone 255-260.5 Caloploicin
245 Didechlorolecideoidin 256-256.5 Vinetorin
245 2,5,7-Trichlorolichexanthone 256-259 Cerevisterol
245 Vesuvianic acid 257-259 (dec.) 2,4,7-Trichloro-3-0-
245-246 Cyclographin methylnorlichexanthone
245-247 Virensic acid 258-260 Phlebic acid B
245-250 (dec.) Protocetraric acid 259-260 Leucotylic acid
245-268 2,5- 259-261 2,5,7-Trichloro-3-0-
Dichloronorlichexanthone methylnorlichexanthone
246-248 (dec.) Ergochrome AA 260 (dec.) Consalazinic acid
246-249.5 Calycin 260-261, softening at 200 Isofulgidin
247 Lecideoidin 260-261 Portentol
247-248 7P-Acetoxyhopan-22-01 260-264 Hypoconstictic acid
247-249 Isovicanicin 260-265 (dec.) a-Acetylsalazinic acid
247-249 Lobodirin 260-280 (dec.) Salazinic acid
248-249 Norvicanicin 261-262 1,8-Dihydroxy-6-methoxy-3-
248-250 5,7 -Dichloro-3-0- (3' -oxobut-l'-enyl)-
methylnorlichexanthone anthraquinone
248-250 Vicanicin 261-263 Friedelin
249 Hopan-15a,22-diol 262 4,4' -Diacetylscabrosin
249-250 4-Chloro-3-0- 262-268 2,7 -Dichloro-3-0-
methylnorlichexanthone methylnorlichexanthone
249-252 Eumitrin Al 262.5 30-Nor-21a-H-hopan-3,22-
249-253 2,5,7-Trichloro-6-0- dione
methylnorlichexanthone 263-264 2a,3 p-Diacetoxystictan -22-
250-251 Fern-9{l1)-en-3,12-dione one
250-251 Iso-norlobaridone 263-264 Hypostictic acid
250-251 (dec.) Methylstictic acid 263-265 6-0-Methylnorlichexanthone
250-252 Fallacinal 264 Cynodontin
250-252 6-0-Methylthiophanic acid 264-266 Trypethelone
250-254 (dec.) Furfuric acid 265 (dec.) 7,7'-Bis-( 1,4,5,8-
250-260 (dec.) Fumarprotocetraric acid tetrahydroxy-3-
>250 (dec.) Canarione ethylnaphtha-2,6-quinone)
251-255 Zeorinone 265 (dec.) Psoromic acid
253 Xanthorin 265-266 Sordidone
253-254 2,5,7- 265-271 Phlebic acid C
Trichloronorlichexanthone 266-268 3P-Acetoxyfern-9( 11 )-en-12-
253-255 3-0-Methylnorlichexanthone one
254-255 1-0-Methylfragilin 267-268 Fragilin
Table 19. Continued
267-275 5,7 -Dichloroemodin 284-286 Demethylchodatin

268 Hopan-16~, 22-diol 285 Acetyl-iso-arborinol
268-270 12a-Acetoxyfern-9(ll)-en- 285 2'-0-Demethylpsoromic acid
3~-ol 285 Papulosin
268-270 Isidiophorin 285-286 Arthogalin
268-285 Arthothelin 285-287 2,4-
>268 Retigeric acid B Dichloronorlichexanthone
269-270 Norsolorinic acid 285-290 5,7-
270-271 (dec.) Mollin Dichloronorlichexanthone
270-272 (dec.) Stictic acid 285-293.5 7-Chloronorlichexanthone
>270 Bellidifiorin 285-295 3-0-Methylasemone
>270 Diacetylgraciliformin 286-287 7-Chloroemodin
>270 Graciliformin 286-287 (dec.) Norstictic acid
>270 Monoacetylgraciliformin 286-288 4,7 -Dichloro-6-0-
>270 (dec.) Substictic acid methylnorlichexanthone
272-273 Menegazzianic acid 287 (dec.) 2,4,5-
272.5-274 3-Dechlorodiploicin Trichloronorlichexanthone
272-274 Emodinaldehyde 287-288 Citreorosein
273-275 3~-Acetoxyhopan-1~, 22-diol 288-289 Eugenitol
274 4,7 -Dichlorolichexanthone 289-290 Nemetzone
274 2a,3~,22a- Triacetoxystictane 290-292 9-Methyl 8-0-
274-275 Simonyellin methylpannarate
274-276 Norlichexanthone 290-292 (dec.) 3-0-Methylthiophanic acid
275-278 5,7 -Dichloro-6-0- 290-293 2,7 -Dichlorolichexanthone
methylnorlichexanthone 290-298 4,7-
276 Stictan-2a,3 ~,22a- triol Dichloronorlichexanthone
276-297 2,5-Dichloro-3-0- 291 Alectosarmentin
methylnorlichexanthone 291-293 (dec.) 4,5-
278-279 Thiophaninic acid Dichloronorlichexanthone
278-279 Thuringione 292-294 (dec.) 3-0-Demethylschizopeltic
278-280 Friedelan-3~-ol acid
279-281 1-0-Methyl-7-chloroemodin 293 (dec.) Rugulosin
280 (dec.) Hyposalazinic acid 294-295 Fumaric acid
280 (dec.) Malonprotocetraric acid 294-296 Chiodectonic acid
280-282 4,5-Dichloro-6-0- 295-296 2,4-Dichloro-3-0-
methylnorlichexanthone methylnorlichexanthone
280-282 Taraxerol 296 (dec.) Variolaric acid
280-283 2-Chloro-6-0- 296-297 4-Chloronorlichexanthone
methylnorlichexanthone 296-299 Retigeric acid A
280-292 Ursolic acid 298-299 2,7-
280-300 (dec.) Connorstictic acid Dichloronorlichexanthone
281-283 3 ~,22a- Diacetoxystictane 298-300 6-0-Methylasemone
282-284 6-0-Methylarthothelin 299-300 2,5-Dichlorolichexanthone
282-284 Methyl pyxinate 300 (dec.) , Aphthosin
283 Stictan-3~,22a-diol 300 (dec.) Cholin sulphate
283-283.5 4,5-Dichlorolichexanthone >300 (dec.) Haematommone
283-284 7-Chloro-3-0- 300 Isolecanoric acid
methylnorlichexanthone >300 4,4'-Disolorir,lic acid
283-285 Arthothelin 300-302 (dec.) Porphyrilic acid
Table 19. Continued
304-305 (dec.) 5-Chloronorlichexanthone 324 Stepsilin

304-305 Parietinic acid 325 2-Chloro-3-0-
307-308 Biruloquinone methylnorlichexanthone
308-309 (dec.) Asemone 328 (dec.) Taurine
309-311 2,7 -Dichloro-6-0- >330 Conhypoprotocetraric acid
methylnorlichexanthone 335-336 Leucotylin
310-312 7-Chloro-6-0- 340 (dec.) Endocrocin
methylnorlichexanthone >350 (dec.) 7,7'-Dichlorohypericin
310-314.5 2-ChloronorlichexanthDne >350 2,2',7,7'-
>310 (dec.) 2,4,7 -Trichloro-6-0- Tetrachlorohypericin
methylnorlichexanthone >350 Thelephoric acid
315 Polyporic acid >360 Flavoobscurin A
>315 1,4,5,6,8-Pentahydroxy-4- >360 Flavoobscurin B,
methylanthraquinone >360 Flavoobscurin B2
320 (dec.) 7-Chlorolichexanthone >360 Oxyskyrin
>320 Asahinin >360 (dec.) Rhodocladonic acid
320, softening at 285 Roccanin >360 Skyrin
>320 1,5,6,8-Tetrahydroxy-3- >360 Skyrinol
methylanthraquinone 363-365 Emodic acid
>320 (dec.) Methyl porphyrilate >365 2,5,7 -Trihydroxyemodin
Table.20. Key for the identification of lichen substances
Lichen substance yellow, orange or red 2

1a Lichen substance colourless 3
2 Compound insoluble in KOH: carotenoids
2a Compound with UV maxima at 290 (4.04) and 376nm (4.46): graphenone
2b Colour of compound not changed with KOH: pulvic acid derivatives
2c Colour of the compound turns to intensive yellow with KOH + NaOCI: usnic acid, isousnic acid
2d Colour of the compound turns to orange with KOH + NaOCI: chromones and xanthones with two OH
groups in meta-position 4
2e Colour of the compound turns to blue or violet: naphthoquinones and anthraquinones 5
5 Compound gives a positive Beilstein test: chlorine-containing anthraquinones
5a Compound gives a negative Beilstein test: naphthoquinones and anthraquinones without chlorine in the
molecule
3 Compound soluble in water: sugars, sugar alcohols and low molecular carbohydrates
3a Compound gives a posItive Lassaigne test: nitrogen containing compounds
3b Compound soluble in NaHC0 3 solution: aliphatic acids, monocyclic aromatic acids, most depsides and
depsidones 6
3c Compound insoluble in NaHC0 3 solution: neutral aliphatic compounds, most terpenoids 7
3d UV maxima of the compound in the range of212-214, 238-259, and 278-338nm: diphenyl ether 8
8 Melting point below 235C: iso-norlobaridone, leprolomin, loxodinol
8a Melting point above 235C: other diphenyl ethers
3e UV maxima in the range of 236-249 (4.53), 256-274 (4.30), and 310-330nm (3.90): dibenzofuranes 9
9 Melting point below 200C: condidymic acid, didymic acid, isodidymic acid, isoschizopeltic acid, melacarpic
acid, methyl ascomatate, 9-methyI4-hydroxy pannarate, methyl 6-0-methyl norascomatate, 3-0-
methylpannaric acid, sub-didymic acid
2.17 Cleavage of Depsides 123
Table 20. Continued
9a Melting point above 200C: other dibenzofuranes

7 Terpenoids
7a Molecular weight (MW) below 160: monoterpenoids
7b MW 234: fukinanolide
7c MW 272-302: diterpenoids
7d MW 370: retigeric acids A and B
7e MW below 430 (except 5a,8a-peroxyergosteryl divaricatinate with MW 620): steroids
7f MW between 424 and 586: triterpenoids
6a UV maxima in the range of 207-225 (4.60),254-275 (4.23), and 282-318 nm (4.00): depsides 8
6b UV maxima in the range of 208-224 (4.46),250-270 (4.13), and 300-333nm (3.75): depsidones 9
8a Compound with a positive p-phenylenediamine reaction: see Table 3
8b Compound with a positive NaOCl reaction: see Table 2
8c Compound with a positive Beilstein test: see Table 4
9a Compound with a positive p-phenylenediamine reaction: see Table 3
9b Compound with a positive NaOCl reaction: see Table 2
9c Compound with a positive Beilstein test: see Table 4
Preferably tert-butanol is used (Bachelor et Table 19 contains the melting points oflichen
al. 1979; Meyappan et al. 1981; Huneck substances and in Table 20 a key for the identi-
1984b): fication of lichen substances is given.
~CO-O OH
HO 5 OH ~COOH
R'
j HO-CIM.),
R ME'
~
5
CO-O-~-ME'
ME' +
H0"6J('0H
HO OH I'COOH
R'
3 Data of Lichen Substances
Data on the occurrence oflichen substances and CD: circular dichroism; = molecular
their physical constants covering the literature
rotation, = [a}M with [a] = spe-
up to 1976 can be found in Culberson's guide 100
(C.F. Culberson 1969, 1970a; C.F. Culberson et cific rotation and M = molecular
al. 1977b). weight; e = molecular ellipticity
Deriv: derivative
3.1 StL: standard lichen, a lichen which con-
General Remarks and Abbreviations tains the corresponding compound
of the Data TLC: thin layer chromatography, RF
retention value; solvent systems:
The lichen substances are arranged in alphabeti- A: toluene: dioxane: acetic acid =
cal order. The molecular weights were calcu- 180:45:5
lated with C 12.01, H 1.008,0 16.00, N 14.008, Cl B: n-hexane: diethyl ether: formic acid
35. 45, P 30.97 and S 32.06. = 130:80:20
B': n-hexane: methyl tert.-butyl ether:
formic acid = 140: 72: 18
Abbreviations
C: toluene: acetic acid = 170: 30
mp: melting point (in 0c), dec. = decom- E: cyclohexane: ethyl acetate = 75: 25
position F: cyclohexane : ethyl acetate = 50: 50
React: reactions with KOH (K), NaOCl G: toluene: ethyl acetate: formic acid =
(Cl), p-phenylenediamine (PD), 139:83 :8
and FeCl3 HPLC: high performance liquid chroma-
UV: ultraviolet spectrum (log E in pa- tography, Rt = retention time
rentheses); MeOH = methanol, (Waters Delta Prep 3000, Finepak
EtOH = ethanol; S = shoulder SIL C1s-1O P column, MeOH:
IR: infrared spectrum HP:H 3 P0 4 = 80:20:0.9), Rj = re-
IH-NMR: IH-nuclear magnetic resonance spec- tention index, Rj (SA) = retention
trum, chemical shifts in 8-values index relative to salazinic acid (S)
!3C-NMR: !3C-nuclear magnetic resonance and atranorin (A)
spectrum, chemical shifts in 8- PC: paper chromatography
values; s = singlet., d = doublet, t = MC: microcrystallization
triplet, q = quartet, quint = quintet Lit: literature
MS: mass spectrum Chemicals: Ac 20 = acetic anhydride, CH 2 N2 =
ORD: optical rotatory dispersion diazomethane
126 3 Data of Lichen Substances
3.2 Allantoin
N-Containing Compounds
4-Acetyl-4'-hexanoylscabrosin O!~
C16HlSNlOS (496.50)
H?N-CO-NH
J- ~)=0
Crystals (H 2 0), mp 226-228C
UV (0.5 n NaOH): 223 nm
IR (KBr): 710, 760, 815, 1015, 1185, 1530, 1660,
1715, 1780 cm- 1
MS, m/z 158 (M+, 8%), 141 (8), 140 (4), 130
OAe
(70),115 (22),99 (4), 87 (62), 60 (25),44 (100), 28
Crystals, mp 213C (75)
MS, m/z 496, 436,380,318 StL: Xanthoria parietina (1.) Th.Fr.
StL: Xanthoparmelia scabrosa (Tayl.) Hale Lit: Solberg 1971
TLC: A: 61, B': 13, C: 43
Lit: Begg et al. 1978 Arthogalin
C24H34Nz06 (446.24)
4-Acetyl-4'-butyrylscabrosin
19
C14H24NIOS (468.45) 18
17
12
13
o H
10
R ..~(sME'
o
ME'
o o 11
H
O~S~~:H
21. : R
Crystals, mp 216.5-217.5C, [am6 - 9600
13C-NMR (CD1CI1): C-2, C-2': 138.27, 138.33, C- ME'~5
3, C-3': 120.62, 120.76, C-4, C-4': 65.20, 65.55, 27 ME'
26
28H"'~
C-5, C-5': 51.44, 51.48,' C-6, C-6': 55.48, C-7,
ME'
C-7': 76.64, C-8, C-8': 37.36, C-9, C-9': 56.84,
5
C-10, C-10': 163.38, C-ll: 170.78, C-12: 20.83,
C-ll': 173.45, C-12': 36.21, C-l3': 18.91, C-14': Threadlike needles (CH1CI2 -n-hexane), mp 285-
13.74 286C
MS, m/z 468, 408, 380, 318 lH-NMR (500MHz,CDCU: 0.90 (3H,d,J=5.9Hz,
StL: Xanthoparmelia scabrosa (Tayl.) Hale Me-4), 0.93 (6H,d,J=6.1 Hz,Me-26,Me-27), 0.95
TLC: A: 57, B': 7, C: 40 (3H,d,J=6.6 HZ,Me-5), 0.96 (6H,d,J=5.9 HZ,Me-
Lit: Begg et al. 1978 10, Me-ll), 2.06 (lH,m,H-3)1 2.18 (lH,m,H-9),
3.2 N-Containing Compounds 127
3.32 (2H,d,J=8.1 Hz,-CH z-15), 3.82 (lH,m,H- lH-NMR (500 MHz,CDCI3): 0.918 (3H,t,J=
14), 3.84 (lH,m,H-2), 4.81 (1H,m,H-24), 5.08 704 Hz,Me-5') , 0.978 (3H,d,J=6.8Hz, Me-6'),
(lH,m,H-8), 5.87 (1H,NH-6), 6.29 (1H,NH-22), 1.04 (3H,d,J=6.9 Hz, Me-5), 1.057 (3H,d,J=
7.13 (2H,d,J=7.3Hz,H-17,H-21), 7.21 (1H,t, 6.9Hz, Me-4), 1.25 (IH,m,H-4'b), 1.53 (1H,m,
J=7.3Hz,H-19), 7.26 (2H,t,J=7.3Hz,H-18, H-4'a), 1.98 (1H,m,H-3'), 2.03 (1H,m,H-3),
H-20) 4.24 (IH,m,H-2), 4.308, (IH,dd,J=I1.4, 5.3Hz,
!3C-NMR (125 MHz,CDCI3): C-1: 172.1, C-2: H-lb), 40493 (1H,dd,J=11.4, 3.1 Hz, H-la), 4.68
60.2, C-3: 28.2, C-4: 17.6, C-5: 19.1, C-7: 169.2, (IH,dd,J=7.5, 5.8Hz, H-2'), 6048 (lH,bd,J=8Hz,
C-8: 8004, C-9: 29.8, C-4, C-5, C-lO, C-11: NH), 6.65 (1H,bd,J=8Hz,NH'), 7.3-7.5 (6H,m,
17.8-18.5, C-13: 169.0, C-14: 5604, C-15: 35.0, H -3"-5",H-3 111 - H-5 111 ), 7.72 (2H,d,J =7.5 Hz,
C-16: 137.9, C-17, C-21: 129.2, C-18, C- H-2111,H-6'"
20:128.5, C-19: 126.7, C-23: 16404, C-24: 79.6, J3C-NMR (75.5 MHz, CDCI3): C-1: 65.3, C-2:
C-25: 26.7, C-26, C-27: 17.8-18.5 54.2, C-3: 29.6, C-4: 19.5", C-5: 19.1", C-l':
MS, m/z446 (M+, 4%),416 (9), 402 (71),331 (38), 172.2, C-2': 5704, C-3': 37.6, C-4': 2504, C-5':
232 (60), 155 (60), 132 (85), 131 (57), 120 (72), 11.4, C-6': 15.5, C-1": 13404, C-2", C-6":
104 (18), 91 (29),83 (12), 72 (100), 55 (51), 43 127.1, C-3", C-5": 128.6, C-4": 131.8,
(18),41 (24),40 (23) C-7". 167.5b , C-ll11: 133.7, C-2"', C-6"': 127.0,
CD (dioxane): positive band at 252 and negative C-3"', C-5"': 12804, C-4111: 131.3, C-7111 :
band at 222 nm 167Ab
StL: Arthothelium galapagoense Hun. et Follm. Values marked with a and b may be exchanged
Lit: Huneck et al. 1995 MS, m/z: 424 (M+, 5%), 381 (15), 368 (3), 303
(14), 249 (2), 236 (24), 218 (40), 208 (12), 190
(66), 176 (29), 146 (25), 122 (9), 105 (100), 77
Arthonin (22)
StL: Arthonia endlicheri (Garov.) Oxner
HPLC: Rl 17
Lit: Huneck et al. 1993b
Choline sulphate (Cholinsulfat)

CsH J3 N0 4 S (183.21)
Crystals (EtOH), mp 300C (dec.)

Needles (MeOH), mp 167-169 C, [ali? - 8.8 IR (KBr): 720, 768, 890, 912, 965, 1042, 1065,
(CHCI3, c 1.18) 1102, 1235, 1265, 1420, 1490, 1515, 1650, 2995,
IR (KBr): 452, 530, 602, 640, 665, 680, 720, 740, 3450, 4500 cm- 1
790, 860, 920, 940, 960, 975, 990, 1020, 1070, lH-NMR (60MHz,DP): 3.20 [s,9H,N(Me)3]'
1140, 1180, 1203, 1290, 1302, 1330, 1352, 1385, 3.72 (m,2H,-N-CH z-), 4046 (m,2H,-CH z-O-)
1465, 1480, 1525 (benzamide), 1575, 1600, 1625 StL: Dermatiscum thunbergii (Ach.) Nyl.,
(benzamide), 1725 (CO), 2875, 2925, 2970, Xanthoria parietina (L.) Th.Fr
3350cm-1 (-NH-) Lit: C.F. Culberson 1969
4,4'-Diacetylscabrosin UV (MeOH): 228nm (4.32)

IR (KBr): 700,760,800,856,928,964, 1030, 1074,
1100, 1130, 1160, 1198, 1290, 1305, 1342, 1362,
1390, 1450, 1490, 1530, 1572, 1598, 1630, 1723,
2960, 3350 cm- 1
AeO IH-NMR (300MHz,CDCI3 ): 4.60 (lH,dd,J=
11.3,3.2 Hz,H-1a), 4.07 (lH,dd,J=11.3, 4.5Hz,
H-1b), 4.7 (lH,m,overl.,H-2), 3.10 (lH,dd,J=
OAe 13.6,6.2 Hz,H-3a), 3.01 (lH,dd,J=13.7,8.1 Hz,
Crystals, mp 262C H-3b), 7.2-7.3 (5H,H-5-H-9), 6.47a (lH,d,
MS, m/z 440,380,320,318 J=6.8Hz,NH), 4.7 (lH,m,overl.,H-2'), 1.75
StL: Xanthoparmelia scabrosa (Tayl.) Hale (3H,m,overl.,H-3'a,H-3'b,H-4'), 1.01 (3H,d,J=
TLC: A: 50, B': 3, C: 33 6.4 Hz,H-5'b), 0.99 (3H,d,J =6.3 Hz,H-6'b), 6.75
Lit: Begg et al. 1978 (lH,d,J=8.5Hz,NH'a) 7.7 (H-2",H-6"), 7.2-7.5
(6H,H-3"-H-5",H-3"'-H-5"'), 7.7 (2H,H-2"',
4,4' -Dibutyrylscabrosin H-6"'); signals marked by a and b may be
exchanged
C26H2SN20S (496.50) 13C-NMR (75.5MHz,CDCI3 ): C-1: 65.1, C-2:
52.1, C-3: 40.8, C-4: 137.3, C-5, C-9: 129.2, C-6,
C-8: 128.3 a, C-7: 126.7, C-1': 173.1, C-2': 50.4,
C-3': 37.4, C-4': 25.4, C-5': 22.6, C-6': 22.1, C-
1": 134.5, C-2", C-6": 127.1, C-3", C-5": 128.7a,
C-4": 131.2, C-7": 167.2b, C-1"': 133.5, C-2"',
C-6"': 127.1, C-3 111 , C-5 111 : 128.5a, C-4111: 131.8,
O-CO-C 3H7
C-7"': 167.7b; signals marked by a and b may
Crystals, mp 196-197C be exchanged
MS, m/z 496, 408, 320, 318 StL: Schismatomma hypothallinum (Zahlbr.)
StL: Xanthoparmelia scabrosa (Tayl.) Hale Hasse
TLC: A: 65, B': 19, C: 46 TLC: RF 0.55 (Merck SiO z, n-hexane: Et20:
Lit: Begg et al. 1978 HCOOH = 20: 30: 6, iodine)
HPLC: RJ 20
Hypothallin Lit: Huneck et al. 1992b
C29H32N20 4 (472.57)
Indolyl-3-acetic acid (Indolyl-3-essigsaure)
5'M'#O~6
Me NH' HN 9V7
6' I I B
~COOH
11/
6'"
5'"
6
C~/7
2'" 6"
3'" 5"
76C~
2"
3"
H
4'" 4" Crystals (CHCI3 ), mp 164-165C

Needles (CHCI3-MeOH), mp 176-177C, [am StL: Ramalina lacera (With.) Laundon
- 22.5 (CHCI 3, c 0.89) Lit: Epstein et al. 1986
3.2 N-Containing Compounds 129
+
Picroroccellin N(Me)3
6 ,-
Mea , I COO-
t 3 4'
HO
or MeO
Needles (EtOAc-MeOH), mp 149-150.2C, [anD

+ 9.0 (MeOH, c 0.112)
UV (MeOH): 272nm (3.05)
IR (KBr): 1120, 1240, 1360, 1460, 1590, 1630,
2500, 2700, 2950, 3300, 3500 cm-1
lH-NMR (400MHz,CD 30D): 2.17 (2H,m,-CH 2-
2'), 2.51-2.77 (2H,m,-CH z-1'), 3.17 [9H,s,-N
Transparent rectangular prisms (EtOH), mp (Me)3], 3.52 (lH,t,H-3'), 3.83 (6H,s,2xMeO-),
190-220, 192-194C, according to the rate of 6.56 (2H,s,H-2,H-6)
heating, [al D + 12.5. (CHCl3) Deriv: N,O- \3C-NMR (100MHz,CD 30D): C-1: 132.4, C-2,
Dimethylpicroroccellin, lustrous, transparent, C-6: 106.8, C-3, C-5: 149.3, C-4: 135.0, C-1':
elongated prisms (EtOH), mp 229C, by methy- 33.3, C-2': 30.5, C-3': 80.0, C-4': 171.8, C-3-
lation of picroroccellin with NaOH-dimethyl OMe, C-5-0Me: 56.7, -N(Me)3: 52.4
sulphate in EtOH StL: Solorina crocea (1.) Ach.
StL: Roccella fuciformis (1.) DC Lit: Kinoshita et al. 1993; Matsubara et al. 1994
Lit: Marcuccio and Elix 1983, 1985
Sticticin
Roccanin
C2sH32N404 (488.57)
CH 2-CO-UCO-HN
HO~COOMe I "
Or ,
H H H
:
NH-CO t1-CO-CH2
H 1D
r
HO~6 N(Me)3
5 $
CIs
Hygroscopic crystals
Crystals (acetic acid), mp 320C, sinters at IH-NMR: 3.12 (2H,m,3'-CH 2-), 3.34 (9H,s,-
285C, [aJii- 92 (DMSO c 1.00) N(Me)3], 3.67 (3H,s,-C0 2Me), 4.43 (lH,dd,
IR(KBr): 1440, 1520, 1625-1675,3330, 3465cm-1 -CH-2'), 6.86 (3H,H-2,H-5,H-6)
StL: Roccella canariensis Darb., R. vicentina MS, m/z 254 (M-Cl), 194 [(HO)2-C6H3-CH=CH-
(Vain.) Vain. C0 2Me]
Lit: Bohmann-Lindgren 1972; Bohmann- Electrophoretic mobility (EM) [Whatman 3MM,
Lindgren and Ragnarsson 1972 40V/cm, pH 2.0 (0.75n HC0 2H), EM = 0.55;
pH 1(3 (0.2 n NH 40H), EM 0.09; pH 6.0
(pyridine: AcOH: H20 = 10: 1 : 989], EM = 0.51
Solorinin
TLC: RF 0.30 (SiO z,CHCl3:MeOH:HCl =
60:20:1)
pc: RF 0.60 (Whatman 3MM, n-butanol: AcOH: Deriv: Xantholamine hydrochloride, mp 95.9 c
HzO = 12:3:5) (dec.), from xantholamine with HCI
Deriv: Hydrolysis of sticticin with 0.2 n KOH at StL: Xanthoria parietina (1.) Th.Fr.
20C yields caffeic acid and trimethyl-amine Lit: Solberg 1974
(odour!)
StL: Lobaria virens (With.) Laundon, Sticta 3.3
fuliginosa (Dicks.) Ach., Sticta sylvatica (Huds.) P-Containing Compounds
Ach.
Lit: Bernard et al. 1980 Phosphatidylcholine (Phosphatidylcholin)
Me 0
Taurine (Taurin) 1+ 11-
CZH7N0 3S (125.13) Me-N-CHz-CHz-O-P-O-R
I II
HzN-CH z-CHz-S0 3H Me 0
R = 14: 0, 15: 0, 16: 0, 16: 1, 17: 0, 18: 0, 18: 1,
Columns (HzO), mp 328C (31rC dec.)
18: 2, 18: 3 (fatty acids)
React: Taurine + phenol + NaOCI ~ blue colour
Deriv: N-Methyltaurine, prisms (MeOH), mp StL: Pseudevernia furfuracea (1.) Zopf
315-316C, by methylation of taurine Lit: Dembitsky et al. 1991a, 1992a
StL: Anaptychia fusca (Huds.) Vain. Anaptychia
runcinata (With.) Laundon, Xanthoria
Phosphatidylethanolamine
parietina (1.) Th.Fr.
(Phosphatidylethanolamin)
Lit: Solberg 1971, 1975b
o
+ 11-
Xantholamine (Xantholamin) H3N-CH z-CH z-O-P-O-R
C6H 13N0 4 (163.16) II
o
R = 14: 0, 15: 0, 16: 0, 16: 1, 17: 0, 18: 0, 18: 1,
2
6 -fxNH
HOCH 2 3 2
OH 18: 2, 18: 3 (fatty acids)
4 1 5 StL: Pseudevernia furfuracea (1.) Zopf
o CH 20H
Lit: Dembitsky et al. 1991a
Crystals
React: brownish colour with ninhydrine
Phosphatidylglycerol
UV (HzO): 188 nm
IR (KBr): 1050, 1105, f215, 1350, 1400, 1450, o
1622, 2880, 2920, 3350 cm- 1 II
lH-NMR (60MHz,D zO): 2.93-3.45 (m,2H, CHz-O-R R = -P-O-R', H, H
4-CH z-), 3.66-3.93 (m,6H,I-H,2-H,5-CHz-, 6- I II
CH z-), 4.68 (s,5H,3x-OH,-NH 2 ) CH-O-R o
MS, m/z: 163 (0.1%), 132 (100), 114 (3.9), 103 I
(3.5), 86 (5.2), 85 (9.0), 84 (8.9), 73 (7.4), 72 CHz-O-R
(8.1), 70 (8.8),68 (11.7), 60 (100), 56 (22.3),41 R' = 14: 0, 15: 0, 16: 0, 16: 1, 17: 0, 18: 0, 18: 1,
(17.9) 18: 2, 18: 3 (fatty acids)
3.5 Polyols, Monosaccharides, Carbohydrates 131
StL: Pseudevernia furfuracea (1.) Zopf StL: Lichina pygmaea (Lightf.) Ag.
Lit: Dembitsky et al. 1991a Lit: C.F. Culberson 1969
3.4 D-Arabitol (D-Arabit)

S-Containing Compounds
CSH120S (152.14)
Dimethyl sulfone (Dimethylsulfon)
C2 H 6 0 2S (94.12) H~T:
o H+OH
II CH 20H
Me-S-Me Prisms (EtOH-acetone), mp 102-103C, [ajbo+

II 12 (saturated borax solution, c 2.00)
o IR (KBr): 735, 780, 860, 870, 880, 910, 950, 1000,
1025, 1050, 1085, 1135, 1205, 1225, 1250, 1320,
Crystals, mp 107-109C 1370, 1440,2960, 3400cm-1
StL: Cladonia deformis (1.) Hoffm. Deriv: Pentaacetyl-D-arabitol, mp 74-75C,
Lit: CF. Culberson 1969 [ajbo+ 37.2 (CHCl3), by acetylation ofD-arabitol
with Acp-pyridine
3.5 StL: Lobaria pulmonaria (1.) Hoffm.
Polyois, Monosaccharides, Lit: CF. Culberson 1969
Carbohydrates
Acroscyphan meso-Erythritol (meso-Erythrit)
Homoglucan with (1 --73), (1 --74) and (1 --76) C4 H lO 0 4 (122.12)

linkages. White powder without melting point, CH 20H
insoluble in cold H 20, [a]D + 176 H+OH
IR (KBr): 845 cm-1 H+OH
StL: Acroscyphus sphaerophoroides Lev. CH 20H
Lit: Shibata 1973 Prisms (MeOH), mp 121.5C
IR (KBr): 720, 870, 890, 920, 970, 1050, 1080,
Arabinose 1210, 1250, 1270, 1300, 1370, 1410, 2850, 2950,
3000, 3350 cm-1
!3C-NMR: 127.8 (CH 20H), 118.7 (CHOH)
Deriv: Tetraacetyl-meso-erythritol, mp 89C,
H by acetylation of meso-erythritol with Ac 20-
Hvt-~H pyridine
StL: Roccella phycopsis (Ach.) Ach.
~
H OH
Lit: CF. Culberson 1969
D-Fructose
Crystals, mp 157-160 C (pyranose form), [albO-
108 (H?O)
Crystals (tOH-HP), mp 190-193C, [abs +

vt-~H 89 (H 2 0)
H~H20H StL: Xanthoria parietina (L.) Th.Pr.

Lit: Garegg et al. 1973
OH H
Prisms (tOH), mp 103-105C (dec.), [ana - l-O-~-D-GaIactopyranosyl- D-ribitol (1-0-~- D-
132 ~ - 92 (H 20, c 2.00) Galactopyranosyl-D-rib it )
Deriv: 1,3,4,5-Tetraacetyl-D-fructose, mp
132C, [a]D - 91 (CHCl3), by acetylation of D- C ll H 22 0 10 (314.29)
fructose with Ac20 CH 20H
StL: Parmelia saxatilis (L.) Ach.
Lit: C.P. Culberson 1969 Hvr-:~-;'-$CH~H
~H OH
GaIactomannan H HO H OH
CH 20H
(1 ~ 6)-linked a-D-Man p, partly substituted at
0-2 with a-D-Gal p units Uncrystallizable, [a]S78 - 3 (H 20)
[aHf + 76 (0.2% NaOH in H20, c 0.2) StL: Xanthoria parietina (L.) Th.Pr.
StL: Neuropogon aurantiaco-ater (Jacq.) Lamb Lit: Garegg et aI. 1973
Lit: Baron et al. 1991
D-Galactose
CH2
Galactomannan B C6H 12 0 6 (180.16)
(1 ~ 6)-linked a-D-mannopyranose with 0H
unsubstituted, monosubstituted with single-
unit side-chains of ~-D-Gal p-(1 ~ 4)-, and dis- H~O~H
ubstituted with ~-D-Gal p-(1 ~ 4)- and
a-D-Man p-(1 ~ 2)-units ~ H HO
StL: Stereocaulon ramulosum (Sw.) Rausch Prisms or plates (tOH), mp 166C, [an + 144
Lit: Baron et al. 1989 ~ + 79.3 (H 20, c 2.00, in 24h).
StL: Parmelia saxatilis (L.) Ach.
O-a-D-Galactopyranosyl-(l ~ 6)-O-~-D Lit: c.P. Culberson 1969
gaIactopyranosyl-(l ~ l)-D-glycerin
ClsH2S013 (416.37) Glucomannan
(1 ~ 6)-linked a-D-Man p chain substituted at
0-2 mainly with side chains of a-D-Man p with
smaller amounts of a-D-Glc p, a-D-Glc p-(1 ~
2)-[a-D-Man p-(1 ~ 4)]-a-D-Man p, and possi-
bly,a-D-Man p-(1 ~ 2)-[a-D-Man p-(1 ~ 4)]-
a-D-Man p units
StL: Tornabaea intricata (Desf.) 0sth.
Lit: Teixeira et al. 1992
3-0-~- D-Glucopyranosyl-D-mannitol (3 -O-~ StL: Peltigera aphthosa (1.) Willd.

D-Glucopyranosyl-D-mannit) Lit: C.F. Culberson 1969
C12H 240 11 (344.31)
Isolichenin
CH 20H
~H'OH00H1~
(C 6H 12 0 6 )n
Linear homoglucan with a(I ~ 3), a(l ~ 4)
~H H H OH
linkages in the ratio 3: 2
HO H H OH HOH 2 C
HQ,
H HO CH 20H
Crystals (EtOH-HP), mp
HOH,tf
(dihydrate), [aj;so - 6 (H 20, C 2.00)
StL: Peltigera aphthosa (1.) Willd.
Lit: C.F. Culberson 1969 ~
HO
~OH'H >-'
D-Glucose
C6H 12 0 6 (180.16)
Hrl:'OH ~~H
HO
Ho'O-lo
'"
HOH2C
HO
H HO
White powder without mp, [ajo + 255
Crystals (H 2 0), mp 147 DC (dec.), [ana + 52.5 React: slightly blue colour with iodine
(H 2 0, c 10.00) IR (KBr): 800, 845,925 cm- 1
StL: Peltigera polydactyla (Neck.) Hoffm. StL: Cetraria islandica (1.) Ach.
Lit: C.F. Culberson 1969 Lit: Shibata 1973
myo-Inositol (myo-Inosit) Lichenin

C6H 12 0 6 (180.16)
(C 6H 12 0 6 )n' MW 20000-40000
H HO Linear homoglucan with ~(I --7 3) ~(1 ~ 4)
linkages in the ration 3: 7
H~H White powder without mp, [a]D + 9 to + 18
~
(H 2 0).
OH H
Crystals (EtOH-H 20), mp 225 DC

Deriv: Hexaacetyl-myo-inositol, mp 200, 216 DC,
by acetylation of myo-inositol with Ac 20-
pyridine
~
CH20HO H
OH H
'--'--'
H HO
HO~ Pco-Jn
HO H
H HO
Amorphous powder without mp, [al D + 201 (2n
NaOH)
IR (KBr): 780, 845, 925 cm- 1
StL: Flavoparmelia caperata (1.) Hale
IR (KBr): 890 cm- 1 Lit: Shibata 1973
StL: Cetraria islandica (1.) Ach.
Lit: Shibata 1973
Peltigeroside (Peltigerosid)
D-Mannitol (D-Mannit) C12 H24 0 11 (344.31)
C6H 14 0 6 (182.17)
a aHaft H OH
HO$CH~OH
H H OH
H HO CH 20H
HO H
CH 20H
H OH
H OH Crystals (EtOH), mp 161-163 DC (monohy-
CH 20H drate), [ana - 61 (H 2 0, c 2.00)
StL: Peltigera horizontalis (Huds.) Baumg.
Lit: c.P. Culberson 1969
Prisms (EtOH), mp 166-167 DC, [al D + 28.3
(saturated borax solution) Pustulan
!3C-NMR: 126.7 (CH 2 0H), 118.7 (2- and 5- (C 6H 12 0 6 )n' MW about 20000
CHCOH), 120.4 (3- and 4-CHOH)
Deriv: Hexaacetyl-D-mannitol, mp 119-120 DC, [-CH 2
[ano+ 25.1 (CHClJ, by acetylation ofD-manni-
tol with Ac2 0-pyridine
StL: Peltigera canina (1.) Willd. HO~
vr-O~KiH2 ~-j H H n
Lit: c.P. Culberson 1969 'H HO HO OH H H
H HO
with 1 O-acetyl group for every 10th to 12th
PC-3-Glucan
glucose unit.
(C 6H 12 0 6 )n, n about 60 White powder without mp, [al D -46 (H20, c 2.00)
IR (KBr): 1250, 1735cm-1 Sucrose (Saccharose)

5tL: Lasallia pustulata (1.) Merat
C12 H 22 0 11 (342.30)
Lit: C.F. Culberson 1969
Ribitol (Ribit)
CSH120S (l52.15)
H~:~H~ OH H
O~HOH
HtCH~~
H HO
H HO 2
H OH HOH 2C 0 H
H OH
CH 20H Prisms (EtOH), mp 185-187 DC, [anD + 66.5
(H2 0)
Prisms (H 20), mp 102 DC Deriv: Octaacetylsucrose, needles, mp 72.3 DC,
StL: Lobaria pulmonaria (1.) Hoffm. [anD + 59.6 (CHCl3 ), by acetylation of sucrose
Lit: C.F. Culberson 1969 with Ac 2 0
Siphulitol (Siphulit) Lit: C.F. Culberson 1969
C7H l6 0 6 (196.20)
D-Tagatose
CH 20H
HO H C6H 12 0 6 (180.16)
HO H
H
H
OH
OH V-0~H
H OH
CH 3
H~H20H
H H
Crystals (MeOH), mp 122-123 DC, [anD - 8
Crystals (EtOH-H 20), mp 134-135 DC, [anD - 2.3
(H 20, c l.5)
(H 20, c 2.19)
Deriv: Tri-O-benzylidenesiphulitol, mp 239:'"
StL: Roccella fuciformis (1.) DC
242 DC, [ano+ 9 (CHCl3 ), by reaction of siphulitol
with benzaldehyde and 50% H 2S04 for 1 h
StL: Siphula ceratites (Wahlenb.) Fr.
Lit: C.F. Culberson 1969 Trehalose
C12 H 22 0 11 (342.30)
SJ-2-I-Glucan
(C 6H 12 0 6 )n' MW about 10000
Linear (1 ~ 3) (1 ~ 4) glucan partially
branched at either 3,4- or 2,3-positions
Amorphous powder, [aJD + 201 (H 20)
IR (KBr): 850cm-1
StL: Stereocaulon japonicum Th.Fr.
Lit: Yokota and Shibata 1978 H HO
Crystals, mp 203C (anhydrous), [an + 197 StL: Dermatocarpon miniatum (1.) Mann
(H 2 0) Lit: C.P. Culberson 1969
Deriv: Octaacetyltrehalose, mp 100-102C, [am
+ 162.3 (CHCI3), by acetylation of trehalose with 3.6
Ac 2 0 Aliphatic and Cycloaliphatic
StL: Lasallia pustulata (1.) Merat Compounds
Lit: C.P. Culberson 1969
3.6.1
Umbilicin Neutral Compounds
CllH22010 (314.29) Acetylportentol

Cl9H2S06 (352.41)
o iCH~OH
H OH
H H OH
CH 20H
H HO 7 10
H OH B 9
CH 3
Prisms (MeOH), mp 223-224C, [al D + 35

Crystals, mp 139-140C, [al D - 81 (H 20, c 2.00)
(CHCI3, c 1.01) IR (KBr): 720, 820, 840, 880, 902,
Deriv: Octaacetylumbilicin, mp 84.5-85.5C,
918,935,962,978, 1020, 1062, 1090, 1108, 1120,
[al D - 22 (CHCI3, c 2.00), by acetylation of
1142, 1160, 1170, 1190, 1222, 1302, 1320, 1350,
umbilicin with Ac20-pyridine
StL: Lasallia pustulata (1.) Merat 1378, 144~ 1460, 1716, 1736, 175~ 2940, 3000,
3550cm-1
lH-NMR (100MHz,CDCI3): 0.77 (d,J=6Hz,3H,7-
Me), 0.79 (d,J=6Hz,3H,9-Me), 1.13 (d,J=6Hz,3H,
Volemitol (V olemit) lO-Me), 1.23 (d,J=6Hz,3H,3-Me), 1.34 (s,3H,1-
Me), 1.40 (m,lH,9-H), 1.56 (d,J=6Hz,3H,5-Me),
C7H l6 0 7 (212.20)
2.08 (m,lH,7-H), 2.10 (s,3H,8-0Ac), 2.35
CH 20H (q,J=6Hz,lH) 2.45 (q,lH,5-H,3-H), 3.80 (q,L=
HO H 10Hz,J2=6Hz,lH,1O-H), 4.42 (bs,lH,4-H), 5.08
HO H (dd,J 1=J2=2Hz,lH,8-H)
HO H MS, miz: 352 (10%), 292 (6), 277 (4), 239 (14),
H OH 194 (8), 181 (9), 179 (12), 163 (7), 152 (20), 141
H OH (22), 83 (41), 43 (100)
CH 20H ORD (MeOH): [l400 + 730, [l302 + 1820, [l246
-1960, [ l227 + 730, [ b!30
Needles (EtOH), mp 151-153C, [am + 2.0 Deriv: Acetyl-2-dihydroportentol, needles, mp
(H 2 0) 193':"'194C, [al D + 78 (CHCI3, c 0.70), by reduc-
IR (Kr): 760, 875, 892, 930, 968,1000,1025,1050, tion of acetylportentol with NaBH4 at 20C for
1060, 1095, 1200, 1260, 1300, 1390, 1425, 1620, 30min
2930, 3000, 3400 cm-1 StL: Roccella JudJormis (1.) DC.
3.6 Aliphatic and Cycloaliphatic Compounds 137
TLC: A: 65, B: 29, C: 45 MC: Fig. 16C

MC: Fig. 60C,D Lit: Huneck et al. 1973; Quinkert et al. 1985,
Lit: Aberhart et al. 1970; Ferguson and Mackey 1988, 1989; Sinha and Keinan 1994
1970
Ethylene (Ethylen)
Alkanes
C2H 4 (26.03)
C13 - and C17-C4o -alkanes have been found in
H 2 C=CH z
lichens
Inflammable gas under normal conditions
Lit: Zygadlo et al. 1993
StL: Ramalina lacera (With.) Laundon
Lit: Lurie and Garty 1991
Aspicilin
C1sH 32 0 S (328.44) 6-Ethyl-6-n-pentyl-pentadecan-4,5,7,8,15-
pentol-15-acetate (6-Ethyl-6-n -pentyl-penta-
decan -4,5,7,8-pentol-15-acetat)
C24H4S06 (432.62)
C,H,
I
Me-CO-O-(CH,)7-CHOH-CHOH-C-CHOH-CHOH-n-C3H7
Leaflets (MeOH), mp 153-154C, [anD + 32 I

n-CsHI!
(CHCl 3, c 2.31)
UV (MeOH): 211 (4.09) Crystals (AcOH-HzO), mp 164-165C
IR (KBr): 720,1060,1240,1375,1440,1465,1735,
IR (KBr): 710, 730, 764, 815, 890, 904, 922, 940,
2850,2915, 3300 cm-l
954, 990, 1010, 1036, 1075, 1120, 1175, 1210,
lH-NMR (60MHz,DMSO-d6): 4.12 (bs,-
1230, 1340, 1362, 1460, 1650, 1704, 2870, 2950,
3350, 3500 cm- 1 CHOH-,OCH2-), 2.00 (s,Me-CO-), 1.30
(-CH z-), 0.87 (t,-Me)
IH-NMR (90MHz,CDCl3-5% CD 30D): 1.27
StL: Alectoria ochroleuca (Hoffm.) Mass.
(3H,d,J=6Hz,18-Me), 1.10-1.80 (20H,bs,10x
CH 2), 3.55 (lH,m,H-5), 3.68 (lH,m,H-6), 4.50 Lit: Solberg 1977
(lH,m,H-4), 5.05 (lH,m,H-17), 6.08, 6.89 (2H,
ABX,JAB=16Hz,J AX=5Hz,JBx=1.9Hz,H-2,H-3) 1-( O-a-D-Glucopyranosyl)-3S,25R-
MS, mlz 328 (M+,0.5%), 310 (0.8), 284 (0.6),227 hexacosanediol [1-( O-a-D-gluco-pyranosyl)-
(4),209 (6), 179 (4), 135 (8), 123 (9), 121 (10), 114 3S,25R -hexacosandiol]
(10), 102 (44), 84 (75), 55 (1bO)
CD (MeOH): ~2S0 - 0.78, ~217 - 3.32 C32H 64 0 4 (512.83)
Deriv: Triacetylaspicilin, needles, mp 118-
119C, by acetylation of aspicilin with AczO-
pyridine at 20C in 24 h
StL: Aspicilia caesiocinerea (Nyl. ex Malbr.)
Arnold
TLC: A: 53, B': 14, C: 11
HPLC: R] 22
Colourless powder, mp 94-99C (dec.) [a]D - 9.5

J3C-NMR (100MHz,CDPD):C-l: 66.4,C-2:
37.8,C-3: 70.1,C-4: 40.2,C-5-C-24: 38.9,C-25: 8'
68.5,C-26: 23.5,C-l': 100.1,C-2': 73.3,C-3': 75.1, Me
o
C-4': 71.8,C-5': 73.5,C-6': 62.7
Deriv: Hydrolysis of 1-( O-a-D-glucopyranosyl)-
3S,25R-hexacosane-diol with 2n-H2S04 gave
1,3S,25R-hexacosanetriol
lH-NMR (400MHz,CDCI3): 1.18 (3H,d,J=6.3Hz, Orange-yellow plates or prisms (acetone), mp
Me-26), 1.48-1.50 (42H,m,-CH 2-4-21), 1.80 163-165C
(2H,m,-CH 2-2), 3.85 (1H,m,H-25), 3.92-4.00 UV (MeCN): 290 (4.04), 376nm (4.46)
(2H,m,-CH 2-1), 3.95 (1H,m,H-3) IR (KBr): 1635, 1652, 1760, 1815, 1859cm-1
13C-NMR (100MHz,CDCI 3): C-l: 59.7, C-2: 38.5, IH-NMR (400MHz,CDCiJ: 1.98 (3H,d,J=0.7Hz,
C-3: 69.5, C-4-C-24: 37.1-38.7, C-25: 66.0,C- Me-9'), 2.19 (3H,s,Me-l0'), 2.39 (3H,s,Me-8'),
26: 22.7 6.51 (1H,d,J=15.4Hz,H-l'), 6.70 (1H,dd,J=
StL: Solorina crocea (1.) Ach. 11.4,14.7Hz,H-3'), 6.98 (1H,dd,J=I1.4,14.7Hz,
Lit: Kinoshita et al. 1993 H-4'), 7.11 (1H,dq,J=0.7,11.4Hz,H-5'), 7.70
(IH,dd,J=I1.4,15.4Hz,H-2')
!3C-NMR (22.5 MHz,CDCI3 ): 9.5, 12.0, 25.7,
Glyceryl trilinolate (Glyceroltrilinolsaureester) 120,7, 135.4, 136.5, 136.8, 137.1, 138.0, 139.8,
141.3, 164.2, 165.8, 199.3
CS7H9S06 (876.33)
MS, m/z 246 (M+, 54%), 281 (17), 203 (27), 173
CH,-O-CO-(CH2)7-CH=CH-CH2-CH~CH-( CH,).-Me (100), 159 (32), 131 (20), 129 (21), 115 (25), 91
I (26)
CH -O-CO-(CH2)7-CH=CH-CH,-CH~CH-(CH,).-Me
StL: Mycobiont of Graphis scripta (1.) Ach. var.
I
CH2-0-CO-(CH')7-CH=CH-CH2-CH~CH-(CH2)4-Me serpentina Meyer
Lit: Miyagawa et al. 1994
Oil
IR (film): 728,1100,1160,1230,1380,1464,1732,
2910, 2960cm-1 n -Heptadecane (n -Heptadecan)
lH-NMR (200MHz,CDCI3 ): 0.87 (9H,t,3x-Me), C17H 36 (240.46)
1.30 (48H,bs,24X-CH 2 - ),2.03 (12H,m,6x=CH-
CH z-), 2.30 (6H,t,3X-CO-CH 2 -), 2.75 (6H,m, CH 3-(CH z)lS-CH3
3x=CH-CH z-CH=), 4.20 (5H,-O-CH z-CHO-
Crystals, mp 22C
CHz-O-), 5.34 (12H,m,6x-CH=CH-)
StL: Pseudocyphellaria crocata (1.) Vain.
TLC: RF 0.64 (SiOz-M~rck PF 254+366, n- Lit: Corbett and Cumming 1971
hexane: EtzO = 4: 1, AcOH-S0 3 HCI, 120C, vio-
let spot)
StL: Umbilicaria antarctica Frey et Lamb Homoheveadride (Homoheveadrid)
Lit: Huneck et al. 1984
C22 H 2S 0 6 (388.18)
Graphenone (Graphenon)
C14H1404 (246.25)
16' 14
ME' 11
ME' 0:r;ME'
~o 4
12
ME'
13
o
10
ME'
ME'
0
O~16
-2Y
OH
12 ' ME'
Rectangular plates (benzene), mp 185C, [a]D +

71 (CHClJ
Amorphous product (from MeOH), [an + 118, IR (KBr): 770, 815, 894, 974, 1000, 1032, 1076,
[a]S78 + 124, [a]S46 + 144, [a]436 + 279, [ab6S + 484 1115, 1178, 1250, 1308, 1338, 1380, 1464, 1720,
(CH 2C1 2, c 0.5) 2996, 3550 cm-'
IR (KBr): 760, 885, 920, 1180, 1260, 1450, 1780, 'H-NMR (360MHz,CDC13 ): 1.04 (6H,d,J=7.0Hz,
1850, 2860, 2920, 2960 cm-' Me-12,Me-12'), 1.19 (6H,d,J=6.33Hz,Me-10,
UV (MeOH): 217, S 240nm Me-lO'), 1.27 (6H,d,J=7 .2Hz,Me-ll ,Me-ll'),
'H-NMR (400MHz,CDC13): 0.85 (3H,t,J=7Hz, 1.57 (2H,ddd,J=2.2,8.6,16.2Hz,H-6b,H-6'b),
Me-5'), 0.93 (3H,t,J=7Hz,Me-4/1), 1.03 (2H,m, 1.63 (2H,ddd,J8b,7=2.6,J 8b,9=10.2, J8b,sa=14.6Hz,H-
H A-2',H A-1/1), 1.12 (1H,m,H B-2'), 1.23 (4H,m,- 8b,H-8'b), 1.68 (2H,ddd,J8a,9=3.1,Jsa,7=11.2,Jsa,sb=
CH 2-3',-CH 2-4'), 1.34 (2H,m,H A -2/1,H A-3"), 14.6Hz,H-8a,H-8'a), 1.90 (2H,tq,J=2.4,7.0Hz,
1.50 (3H,m,H A -1',H B-2/1,H B-3/1), 1.77 (1H,t,J= H-4,H-4'), 2.73 (2H,dd,J=4.0,16.0Hz,H-6a,H-
12Hz,HA -9), 2.00 (1H,m,H B-1/1), 2.20 (4H,m, 6'a), 2.79 (2H,dq,J=7.3,1O.5Hz,H-2,H-2'), 3.71
H c 3,HA-4,H-8,HB-1'), 2.41 (1H,qint.,J=5Hz, (2H,dd,J=2.5,10.5Hz,H-3,H-3'), 4.89 (2H,ddq,
H-7), 2.85 (1H,dd,J=12Hz,3Hz,H B-9), 3.15 (2H, J=4.9,6.2,9.0Hz,H-9,H-9'), 5.04 (2H,dq,J=3.5,
m,H B-3,HB-4) 10.0Hz,H-7,H-7'), 5.21 (2H,dd,J=2.2,8.5Hz,H-
MS, m/z 388 (M+, 4%), 342 (1),264 (4),194 (100), 5,H-5')
176 (9), 166 (11), 151 (7), 149 (7) 138 (8), 125 !3C-NMR (CDC1 3 ): C-1,l': 175.57, C-2,2': 44.37,
(20), 121 (10), 93 (7),91 (9), 83 (9), 79 (11),69 C-3,3': 75.83, C-4,4': 36.42, C-5,5': 69.47, C-6,6':'
(16), 55 (19),43 (19),41 (30) 33.54, C-7,7': 68.74, C-8,8': 38.16, C-9,9': 67.10,
TLC: A: 77, B: 51, B': 52, C: 76 C-10,10': 20.45, C-ll,l1': 13.91, C-12,12': 11.15,
StL: Cladonia polycarpoides Nyl. C-13,13', C-15,15': 170.12, C-14,14', C-16,16':
Lit: Archer and Taylor 1987' 20.96
MS, mlz 642 (33%, M-H 20), 600 (19), 582 (54),
572 (9),540 (29), 527 (24),522 (10), 514 (11),480
Lepranthin
(9), 460 (16), 433 (26), 415 (26), 373 (37), 355
C32 H s2 0'4 (660.74) (52), 331 (60), 313 (60), 306 (27), 299 (45), 295
(27), 2i1 (74), 270 (36), 266 (26), 257 (98), 253
(49),229 (56),228 (49),210 (82), 197 (67), 193
(65), 192 (56), 169 (100), 168 (87), 157 (87), 143
(52), 140 (88), 139 (90)
CD (EtOH): ~E-4.17 (216nm) Portentol

Deriv: Lepranthone, mp 200-201 C (MeOH), by
C17H Z6 0 S (310.38)
oxidation of lepranthin with Jones' reagent
StL: Arthonia impolita (Ehrh.) Borrer
Lit: Polbom et al. 1995
Methyl protolichesterinate
(Protolichesterinsauremethylester )
CZOH3404 (338.47)
tt
Prisms (MeOH), mp 260-261 DC, [a]D + 21
20 6 Ha (CHC13, c 1.02)
MeOOe 5 H
3 b IR (KBr): 670, 702, 725, 815, 837, 868, 908, 928,
",4 1 0 96~ 92~ 96~ 97~ 98~ 1016, 1034, 106~ 109~
Me
19
:" 0 1112, 1124, 1134, 1170, 1190, 1244, 1255, 1305,
1320, 1350, 1362, 1374, 1405, 1450, 1478, 1720,
Plates (n-hexane), mp 40-41C, laW + 4.9 1754, 2860, 2910, 2940, 3450 cm-1
(CHC13, c 2.61) IH-NMR (100MHz,CDCIJ: 0.97 (6H,d,J=6Hz,
UV (EtOH): 209 nm (3.96) Me-9), 1.17 (3H,d,J=6Hz,Me-10), 1.31 (3H,d,J=
IH-NMR (300MHz,CDC13): 0.88 (3H,t,J=7.5Hz, 6Hz,Me-3), 1.38 (s,3H,Me-1), 1.40 (lH,m,H-9),
Me-19), 1.26 (22H,bs,-CH z-7-17), 3.57 (lH,dt, 1.54 (3H,d,J=6Hz,Me-5), 1.86 (1H,d,J=2Hz),
J3,4=5.7Hz,J 3,zo=3Hz,H-3), 3.80 (3H,s,-COOMe), 1.94 (lH,q,J=6a.2Hz), 2.32 (lH,q,J=6Hz), 2.59
4.80 (lH,dt,J4,3=5.7Hz,J4,7=7Hz,H-4), 5.91 (lH,d, (lH,q,J=6Hz), 3.58 (lH,q,J=6a.l0Hz), 3.88 (lH,
J=2.7Hz,H-5 a ), 6.40 (lH,d,J=3Hz,H-5 b ) qd,J=6a.lOHz), 4.42 (lH,bs,H-4)
MS, m/z 338 (M+,760/0), 309 (13),279 (100), 261 MS, m/z: 310 (M+,250/0), 197 (65), 181 (34), 141
(9),211 (10),169 (52),156 (63),128 (32),109 (9) (100),85 (80),83 (100),69 (78), 58 (65),57 (57),
StL: Cetraria islandica (1.) Ach. 43 (100)
Lit: Solberg 1986; Huneck and Takeda 1992 ORD (MeOH): [<1>]400 + 260, [<1>]323 + 170, [<P]303 +
1275, [<Pbsl - 945, [1Z37 - 340, [1Z19 - 5690
n-Nonacosan-IO-ol CD (dioxane): ~E321 - 0.226, ~E30S - 0.113, ~E300 +
0.181, ~E290 + 0.294, ~E2S1 + 0.256, ~E273 + 0.173,
Cz9 H60 0 (224.29) ~EZ34 + 1.93
Me-(CH z)s-CHOH-(CH z)IS-Me Deriv: Portentone, prisms (MeOH), mp 153-
154 DC, [a1D + 50 (CHC13), by oxidation of
Prisms (EtOH), mp 83-84C portentol with Jones' reagent at 20 DC in 1 min
MS, m/z 406 (M-H zO+,100/0), 297 (42), 278 (5), StL: Roccella galapagoensis Follm.
237 (82), 209 (4), 195 (6), 181 (8), 167 (11), 157 Lit: Aberhart et al. 1970
(71), 139 (29), 138 (23), 111 (51), 97 (77), 83 The following aliphatic compounds have been
(100) detected in small amounts in Evernia prunastri
Deriv: n-Nonacosan-10-one, mp 74-75C (1.) Ach.: nonane, decane, undecane, dodecane,
(EtOH), by oxidation of n-nonacosan-10-ol with tridecane, tetradecane, pentadecane, 2-me-
Jones' reagent thylpentadecane, hexadecane, hepatdecane,
StL: Parmelia omphalodes (1.) Ach. pentadec-l-ene, (Z)-heptadeca-l,8-diene, (Z),
Lit: Tabacchi et al. 1987 (Z)-heptadeca-l,8,l1-triene" dec-l-yne, cyclo-
hexanol, hexadecanol, heptadecanol, mesit- Acarenoic acid (Acarenosaure)

yloxide, 4,6-dimethyldec-4-en-3-one, 2-meth-
C17 0 ZS 0 4 (296.40)
yldecaline, 3-methylundec-5-ene, tetradec-1-
ene, 4,8-dimethyltridecane, 2-methyltridecane,
methyl trans-dodec-9-enoate, tetradec-1-ene,
3,5-dimethyldec-3-en-2-one
Lit: Gavin et al. 1978
3.6.2
Acids Plates (benzene), mp 130-132C, [a]b4 - 84.3
(CHC13, c 0.265)
Acaranoic acid (Acaranosaure) UV (MeOH): 219 (3.42)
IR (KBr): 684, 718, 810, 928, 954, 1000, 1048,
C17H3004 (298.41) 1080, 1102, 1136, 1178, 1196, 1276, 1310, 1360,
1398,1422,1442,1470,1614 (C=CH z), 1670, 1720
(o-lactone-CO), 2900, 2960, 3500cm-1
lH-NMR (270MHz,CDC13 ): 0.88 (3H,t,Me-15),
1.26 (l6H,bs,CH 2-7-14), 2.03 (lH,m,H a-4), 2.21
(lH,m,H e-4), 3.69 (lH,m,H-3), 4.23 (lH,m,H-
5),5.93 (lH,d,H a-16), 6.64 (lH,d,Hb-16)
Deriv: Addition product of acaranoic acid with
Plates (diethyl ether), mp 154-155 C [ali? - 38.9 CHzN z, mp 48-48.5C (MeOH-HzO), [am +
(CHCI3: MeOH=l : 1, c 1.36) 238.5 (CHCI3), by treatment of acaranoic acid
UV (MeOH): 210nm (2.85) with CH2N2 in Et 20 at room temperature for 4h
IR (KBr): 688, 722, 748, 814, 920, 960, 990, 1000, CD (MeOH): .6.Z68 + 0.20, .6.ZI6 - 5.23
1050, 1102, 1140, 1150, 1178, 1196, 1228, 1250, StL: Pleopsidium chlorophana (Wahlenb. ex
1270, 1304, 1330, 1362, 1384, 1398, 1428, 1448, Ach.) Hafellner
1470, 1618, 1678, 1716,2800, 3500cm-1 MC: Fig. 14
lH-NMR (270MHz,CDCI3:CD30D=4: 1, 60C): Lit: Huneck and H6fie 1980
0.89 (3H,t,Me-15), 1.26 (l6H,bs,CH z-7-14),
1.35 (3H,d,Me-16), 1.40-1.60 (2H,m,CH z-6),
19-Acetoxylichesterinic acid
1.75 (lH,dt,H a-4), 2.20 (lH,dt,H e-4), 2.58
(19-Acetoxylichesterinsaure)
(lH,td,H-3), 2.76 (lH,dq,H-2), 4.31 (lH,m,
H-5) C21H3406 (382.23)
MS, m/z 298 (M+,45%), 280, (42), 262 (29), 252
(850), 157 (77), 139 (100), 111 (97) 6 5
CD (MeOH): .6.222 + 2.23 HOOne
~ 20 8 3 2
Deriv: Methyl acaranoate, mp 58-59C (pen- Me-CO-O,......-/'0...-...,.-/'0........,-/"0-......,-- ".......-- "......,-- "...... 4
.'
0 1 0
tane), [am - 31.1 (CDCI3), by methylation of 19 7
acaranoic acid with CH 2N z
StL: Pleopsidium chlorophana (Wahlenb. ex Crystals (n-hexane), mp 98-99C, [am + 18
Ach.) Hafellner (CHCI3)
MC: Fig. 14 IR (KBr): 625, 705, 715, 760, 765, 880, 945, 980,
Lit: Huneck and H6fie 1980 1009, 1040, 1135, 1155, 1215, 1250, 1330, 1345,
1375, 1430, 1475, 1480, 1663, 1705, 1740, 2860, MS, m/z: 382 (M+,7%), 364 (3), 340 (3), 339 (7),
2920, 3080 cm- 1 322 (14), 309 (7),304 (12), 277 (17), 239 (10),225
lH-NMR (CDCI3): 1.25 (24H,m,-CH 2-7-18), (9),211 (17),209 (10),207 (7), 206 (10),193 (17),
2.08 (3H,s,Me-21), 2.25 (3H,d,J=2Hz,Me-5), 192 (10), 181 (14), 179 (10), 178 (12), 168 (14),
4.10 (2H,t,J=6Hz,-CH 2-19), 5.15 (1H,tq,Jt=6Hz, 165 (24), 155 (34), 142 (12), 125 (14), 123 (14),
Jq=2Hz,H-4), 8.38 (1H,s,-COOH) 111 (17), 109 (17), 97 (34), 95 (28), 83 (45), 81
13C-NMR (CDCI3): C-1: 173.0, C-2: 139.2, C-3: (31),69 (69),67 (58), 57 (55), 55 (83),43 (100)
147.4, C-4: 81.5, C-5: 10.4, C-6: 165.3, C-7: 32.3, StL: Neuropogon trachycarpus Stirt.
C-8: 24.6, C-9-C-17: 29.1-29.4, C-18: 24.6, C- TLC: RF 0.40 (silica gel 60 F 254, toluene: AcOH =
19: 60.6, C-20: 174.7, C-21: 30.9 17:3)
MS, m/z: 382 (M+,20%), 364 (6), 340 (5), 339 (3), Lit: Ghogomu and Bodo 1982
322 (17), 309 (8),304 (11), 277 (15), 239 (13),225
(22),211 (13),209 (6),207 (6),206 (8),193 (17),
allo-Protolichesterinic acid
192 (9), 181 (6), 179 (9), 178 (8), 168 (16), 155
(allo-Protolichesterinsaure)
(31), 142 (18), 125 (13), 123 (12), 111 (26), 109
(16),97 (50), 95 (26),83 (61),81 (28),69 (68),67 Cl9H3204 (324.45)
(30),57 (47), 55 (90),43 (100) 6
Deriv: 19-Hydroxylichesterylic acid, mp 89- H0 2C
91 DC, by saponification of 19-acetoxyliche- 19 16 8 3
sterinic acid with NaOH in EtOH Me 7 4 01 0
StL: Neuropogon trachycarpus Stirt. Plates (AcOH), mp 107 DC, [a.m - 102 (CHCI3)
TLC: RF 0.46 (silica gel 60 F 254, toluene: AcOH = IR (KBr): 716, 764, 820, 880, 946, 970, 1020, 1080,
17: 3) 1130, 1210, 1244, 1250, 1316, 1350, 1430, 1470,
Lit: Ghogomu and Bodo 1982 1650, 1700, 1730,2900,2950,3100, 3500cm-1
lH-NMR (270MHz,CDCI3): 0.88 (3H,t,J=6Hz,
19-Acetoxyprotolichesterinic acid (19- Me-19), 1.26 (22H,bs,-CH 2-8-18), 1.70 (2H,m,-
Acetoxyprotolichesterinsaure) CH z-7), 4.02 (lH,ddd,J3,4=7Hz,J3,s=2.4Hz,H-3),
4.66 (1H,ddd,J4,3=7.5Hz,J4,r=7.5Hz,H-4), 5.89
C21H3406 (382.23) (2H,d,Js,3=2.5Hz,=CH 2-5)
StL: Cetraria ericetorum Opiz
6 5 Lit: Carlson and Oyler 1976; Huneck et al. ~979
H0 2C CH2
21
20 18 16 14 12 10 8 3\---42-
Me-CO-O~ .;Z.,.,ho Angardianic acid (Angardiansaure)
19 17 15 13 11 9 7' 4 0 1
Cl9H3604 (328.48)
Crystals (acetone-H 20), mp 94-96 DC CHXCOOH
IR (KBr): 1250, 1660, 1718, 1740, 2860, 2920,
3080cm-1
n-C 14 H z9 COOH
lH-NMR (CDCU: 1.25 (24H,m,-CH z-7-18),
2.05 (3H,s,Me-21), 3.65 (1H,dt,J d=6Hz,J t=3Hz, Physical data unknown
H-3), 4.10 (2H,t,J=6Hz,-CH 2-19), 4.80 (lH,dt, MS, m/z 328 (M+,l%), 310 (8),292 (8),282 (22),
Jd=Jt=6Hz,H-4), 6.05 and 6.50 (2H,d,J=2.7 and 246 (30),255 (37),238 (12), 170 (48), 156 (55),
3.2Hz,=CH 2-5), 8.40 (lH,s,-COOH) 138 (26), 132 (93), 114 (100).
StL: Leproloma angardianum (0vstedal) Crystals (MeOH-H 20), mp 132-133.5 c, [am-

Laundon 15.5 (CHCl3, c 0.9)
Lit: Leuckert and Kiimmerling 1991 IR (KBr): 670, 720, 730, 800, 850, 868, 950, 995,
1110, 1140, 1210, 1240, 1250, 1270, 1290, 1375,
1410, 1445, 1462, 1690, 1730, 2900, 2950,
Bourgeanic acid (Bourgeansaure)
3560cm-1
C22 H 42 0 S (386.56) IH-NMR (220MHz,acetone-d6 ): 0.88 (3H,t,
Me-), 1.29 [26H,bs,-(CH2)!3-]' 2.67 (1H,t,H-4),
2.77 (2H,d,J=16Hz,-CH 2-2), 3.61 (3H,s,-
COOMe)
MS, m/z: 402 (M+,l %) 384 (0.2), 371 (0.3), 366
(0.8), 329 (9),320 (7), 184 (16), 166 (17), 152
(17), 129 (20), 116 (51), 98 (16), 71 (22),69 (27),
59 (15), 57 (51),43 (100),31 (14)
Needles (n-hexane, or MeOH-H 20), mp 125-
Deriv: Dimethyl caperatate, needles (MeOH),
126C, [aH} + 7 (CHCl3 )
mp 56.5-57.5 c, from caperatic acid with CH2N 2
IR (KBr): 750, 780, 850, 910, 928, 950, 975, 990,
StL: Flavoparmelia caperata (1.) Hale
1032, 1048, 1078, 1100, 1118, 1150, 1190, 1220,
TLC: A: 4, B: 27, B': 32, C: 6
1262,1310, 1398,1462, 1728, 2980, 3460cm-1
MC: Fig. 14B,C
IH-NMR (60MHz,CDCl3 ): 0.70-2.00 (36H,bs,
Lit: Brandange et al. 1975
Me-,-CHz-,-CH-), 2.72 (2H,m,2x=CH-COO-),
3.75 (lH,q,=CH-OH), 5.23 (1H,q), 6.77 (2H,s,-
OH,-COOH) Caproic acid (Capronsaure)
MS, mlz 387 (M+H), 287, 269, 258, 185, 167
Deriv: 3-Hydroxy-2,4,6-trimethyloctanoic acid, C6H 12 0 2 (116.16)
oil, bpO.9 154C, [ani - 3.2 (CHCl3 ), by saponifi-
cation ofbourgeanic acid with KOH in EtOH CH 3- ( CH2)4-COOH
StL: Ramalina bourgeana Mont., Ramalina Oil, mp -2C, bp 205 c, n~n .41635
evernioides Nyl. StL: Evernia prunastri (1.) Ach.
TLC: A: 54, B: 61, B': 62, C: 48 Lit: Gavin and Tabacchi 1975
MC: Figs. 59D, 60A,B
Lit: Follmann and Huneck 1968; Bodo et al.
1973; Bruun 1973; Bodo 1975; White and Caprylic acid (Caprylsaure)
Johnson 1990, 1994
CSH l6 0 2 (144.21)
Caperatic acid (Caperatsaur'e) CH3-(CH2)6-COOH

C21 H 3S 0 7 (402.51) Crystals, mp 16C, nbo 1.4285
StL: Evernia prunastri (1.) Ach.
Lit: Gavin and Tabacchi 1975
Constipatic acid (Constipatsaure)
C21H 36 0 S (368.25)
ti
6 5 7.5Hz,-CH 2-19), 3.02 (1 H,dq,J2,3=1OHZ,J2,S=
H0 2 C CH 3
OH 3 2 7.2Hz,H-2), 3.20 (1H,dd,J3,2=10Hz,J 3,4=8Hz,H-
21 b
CH 3-C-(CH 2)13 4 0 1 0
3),4.67 (1H,ddd,J4,3=8Hz,J4,7=5 a. 8.5Hz,H-4)
~ !3C-NMR (CDCI3): C-1: 173.04, C-2: 36.65, C-3:
H 51.73, C-4: 77.47, C-5: 14.41, C-6: 177.33 C-7:
White flakes (AcOH), mp 108-109C, [aH]- 24 31.17, C-8: 25.58, C-9-C-17: 29.14-29.43, C-18:
(CHCI3 ) 23.95, C-19: 43.80, C-20: 209.82, C-21: 29.54
IR (Nujol): 1702, 1740, 3400 cm-l MS, mlz 368 (M+,16%), 353 (6),339 (4),326 (10),
lH-NMR (100MHz,CDCI3): 1.18 (3H,d,J=6Hz, 325 (12), 293 (34), 292 (12), 275 (38), 265 (18),
Me-21), 1.27 [26H,bs,-(CH2)!3-]' 2.10 (3H,d,J= 247 (16), 219 (12), 191 (16), 179 (32), 178 (22),
2Hz,Me-5), 3.88 (lH,m,H-20), 5.14 (1H,m,H-4) 137 (18), 123 (22), 109 (36), 97 (38), 95 (58), 85
MS, m/z: 368 (3%),353 (19),350 (32),332 (12), (20), 83 (38), 81 (56), 71 (56), 69 (68), 67 (42), 59
325 (14), 324 (49), 306 (12),305 (11),304 (12), (22),58 (82), 55 (100)
280 (24),279 (100),261 (13), 179 (12),168 (11), CD: Ll +0.058 +0.104 +1.38 +0.125
165 (15), 155 (50), 151 (11),142 (42), 14i (10), 280 260 221 192nm
139 (10), 137 (10),123 (15), 111(19),109 (15),97 (acetonitrile)
(30),95 (25), 83 (34),81 (21),71 (19),69 (44), 67 Deriv: (-)-Methyl dihydropertusarate, needles
(24),57 (30), 55 (55),45 (40),43 (10) (from MeOH) of mp 61-62C and [an4 - 67.8
Deriv: Methyl constipatate, mp 52-53C, by (CHCI3, c 0.84), from the acid with CH2N2in Et 20
methylation of constipatic acid with CH2N2 StL: Pertusaria albescens (Huds.) Choisy et
StL: Xanthoparmelia constipata (Kurok. et Fils.) Werner
Elix et Johnston TLC: A: 42, B: 36, B': 36, C: 35
TLC: RF 0.35 (silica gel, n-hexane: Et20: HCOOH Lit: Huneck et al. 1986
= 13:8:2). A: 31, B': 27, C: 29
Lit: Chester and Elix 1979b Fumaric acid (Fumarsaure)
C4H 40 4 (116.07)
(-)-Dihydropertusaric acid
[(-) -Dihydropertusarsaure) H~ /COOH
C=C
C21H360S (368.50) HOOC/ ~H
6 Crystals, mp 294-295C
HOOC
IR (KBr): 1000, 1210, 1290, 1440, 1630-1700,
~ 8 2500-3300 cm- 1
Me 20 19 17 9 7 4 0 1 0 IH-NMR (60MHz,DMSO-d6-CDCI3 ): 6.33 (2H,
s,=CH), 11.00 (2H,s,-COOH)
Needles (MeOH-HzO), mp lOS-107C [aW- MS, mlz 116 (M+,36%), 98 (100), 71 (45),54 (18),
74.9 (MeOH, c 2.15) 44 (20)
UV (MeOH): 207nm (2.74) StL: Dictyonema glabratum (Fr.) D.Hawksw.
IR (KBr): 702, 726, 860, 878, 988, 1014, 1090, Lit: C.F. Culberson 1970a
1112, 1194, 1198, 1242, 1318, 1366, 1418, 1470,
1736, 2970, 3180 cm-1
lH-NMR (400 MHz,CDCI3): 1.26 (3H,d,J S,2=
7.2Hz,Me-5), 2.16 (3H,s,Me-21), 2.41 (2H,t,J=
Hexa-(a-hydroxyisovalerate), [Hexa-(a-
hydroxyisovalerat) 1
C30HS0013 (618.70)
HO-CH-COO-CH-COO-CH-COO-CH-COO-CH-COO-CH-COOH
I I I I I I
CH CH CH CH CH CH
/~ /~ /~ /~ /~ /~
Me Me Me Me Me Me Me Me Me Me Me Me
This compound is only described as its methyl IH-NMR (CDC1 3): 1.26 [24H,m,-(CH z)12-]' 2.17
ester, C31HS2013' gum of [al D + 44 (CHC1 3 ) (3H,s,Me-21), 2.25 (3H,d,J=2Hz,Me-5), 2.45
IH-NMR (60MHz,CDC13): 1.08 (36H,d,J=6Hz,- (2H,t,J=7Hz,-CH z-19), 5.13 (1H,m,H-4), 7.95
CH(Me)2)' 2.34 [6H,bm,-CH(Me)z]' 3.73 (3H,s,- (IH,s,-COOH)
COOMe), 4.13 (1H,d,J=4Hz,-CHOH-), 5.01 (6H, 13C-NMR (20MHz,CDC13 ): C-l: 172.3, C-2:
d,H-C-OCOR) 139.0, C-3: 146.6, C-4: 81.0, C-5: 10.5, C-6:
StL: Cladonia sulphurina (Michx.) Fr. 165.0, C-7: 32.2, C-8: 24.2, C-9-C-17: 28.8-
Lit: Bruun 1976b 29.1, C-18: 23.4, C-19: 43.4, C-20: 210.1, C-21:
29.1
MS, m/z 366 (M+,28%), 349 (6), 348 (25), 308
Isomuronic acid (Isomuronsaure), (25), 307 (15), 291 (6), 290 (11), 253 (18), 251
dehydroconstipatic acid, neuropogonic acid (11), 239 (18), 225 (24), 211 (18), 193 (6), 155
C21 H 340 S (366.24) (57), 142 (12), 141 (11), 123 (14), 111 (14), 109
Isomuronic acid has been found in lichens in (20),97 (31), 95 (35), 89 (17),87 (29),85 (31),71
both antipodes (49),69 (62), 58 (61),55 (71),43 (100)
StL: Neuropogon trachycarpus Stirt.
TLC: Rp 0.43 (silica gel Merck 60 F 254,
toluene: AcOH = 85: 15). A: 40, B': 35, C: 35
Lit: Huneck et al. 1979; Chester and Elix 1979b;
Bodo and Molho 1980
Isorangiformic acid (Isorangiformsaure)

C21 H 38 0 6 (386.51)
(- )
H0 2C /1'"
i'" . .
1
3
H
C0 2Me
(+)-Isomuronic acid: crystals (acetone-H20), n-C 14H29 : C02H

mp 108-109C, [aW + 24.7 (CHCU H
(-)-Isomuronic acid: needles (benzene), mp 91- Plates (MeOH-HzO), mp 83-85C, [aW + 5.2
92 C, [am - 23.5 (CHC1 3 ) (MeOH,'c 2.455)
UV (EtOH): 227nm (4.1) IR (KBr): 670, 720, 800, 858, 954, 1040, 1060,
IR (KBr): 710, 720, 766, 885, 1215, 1430, 1475, 1200, 1230, BOO, 1436, 1470, 1694, 1726, 2900,
1665, l705, 1715, 1740,2850, 2920cm-1 2970, 3500 cm-1
IH-NMR (100MHz,CDCl3): 0.83 (3H,t,Me-), MS, m/z (Me-ester): 368 (5%), 324 (5), 187 (22),
1.22 (24H,bs,-(CH 2)12-), 2.40-3.00 (4H,m,2x- 173 (38), 159 (27), 145 (62), 131 (100), 117 (70),
CH 2-), 3.20-3.40 (2H,m,H-2,H-3), 3.68 (3H,s,- 105 (75),91 (75), 79 (63), 68 (38)
COOMe), 9.78 (2H,bs,2x-COOH) StL: Cladonia portentosa (Dufour) Coem.
MS, m/z: 368 (M-H 20,69%), 350 (55), 336 (57), Lit: Dertien et al. 1977
322 (92), 308 (79),294 (79), 290 (84),280 (69),
264 (79), 228 (69), 214 (87), 210 (87), 200 (90),
Lactone carboxylic acid from Lecanora
196 (94), 182 (100), 170 (94), 168 (99), 156 (89),
rupicola (Lactoncarbonsaure aus Lecanora
154 (99), 140 (92), l26 (91), 112 (85), 98 (92), 84
rupicola)
(92)
Deriv: Isorangiformic acid anhydride, mp C17H 30 0 4 (298.41)
92-94C, [a]64 + 13.4 (CHCl3, c 1.74), from
isorangiformic acid with acetylchloride under H02C1---r'CH 3
reflux for 2 h
StL: Lecanora stenotropa Nyl. n-C ll H23
~O~O
Lit: Huneck 1982
Microcrystals (n-hexane), mp 103-107C
IR (CHCl3): 1705, 1723, 1765,2875, 2950 cm-l
Jackinic acid (Jackinsaure)
MS, m/z: 298 (12%),280 (20), 262 (15),252 (32),
Cl9H3406 (358.46) 235 (20),225 (100),207 (32), 154 (48), 143 (70),
132 (30), 114 (68), 57 (95)
StL: Lecanora rupicola (1.) Zahlbr.
Lit: Devlin et al. 1971
Lichesterinic acid (Lichesterinsaure)

Physical data unknown Cl9H3204 (324.45)
MS, m/z 340 (M-H 20), 322 (M-2H 20), 309, 294,
280,266,262,252,234,190,172
StL: Lepraria jackii T0nsberg 18 16 14 12
Lit: Kiimmerling et al. 1994. 17 15 13 11
Plates (EtOH), mp 123-124C [am - 32.6

Lactone carboxylic acid from Cladonia impexa
(CHCIJ
(Lactoncarbonsaure aus Cladonia impexa) UV (MeOH): 227nm (4.17)
C21 H 3S 0 4 (354.51) IR (KBr): 710, 722,770,900,955,990,1010,1022,
1135, 1150, 1215, 1320, 1350, 1380, 1430, 1470,
1690, 1725,2850,2930, 3500 cm-l
IH-NMR (270 MHz,CDCl3): 0.88 (3H,t,J=6Hz,
Me-19), 1.27 [22H,-(CH 2)1l-]' 1.70 (2H,m,-
CH~-7), 2.24 (3H,d,J=2Hz,Me-3), 5.13 OH,
ddd,J4,3=5Hz,J4,7=2Hz,H-4)
Melting point and optical rotation unknown I3C-NMR (20.1 MHz,CDCl3): C-1: 172.8, C-2:
IR: 2920, 2960 cm-l 140.3, C-3: 146.9, C-4: 81.5, C-5: 11.0, C-6:
167.0, C-7: 32.8, C-8: 24.8, C-9-C-16: 29.4, 29.7,

C-17: 31.9, C-18: 22.7, C-19: 14.1
MS, m/z 324 (M+), 306, 280, 279
CD (MeOH): 1l292+0.11, llE25s-0.56, llE230+4.15,
1llss-3.69
Deriv: Methyl lichesterinate, mp 53-54 DC,
[a]b4 - 28.1, from lichesterinic acid with CH 2N z Crystals (MeOH-HzO), mp 125 D C, [alii - 15.4
StL: Cetraria ericetorum Opiz (dioxane, c 0.06)
MC: Fig. 14D IR (KBr): 715, 725,1215,1250,1680, 1705, 1730,
Lit: Huneck and Takeda 1992 3500cm-1
IH-NMR (60MHz,acetone-d6): 1.4 [26H,bs-
()-Lichesterylic acid [()-Lichesterylsaure] (CH Z)13-]' 2.10 (3H,s,Me-20), 2.43 (2H,t,J=7Hz,-
CH z-18), 2.67 (1H,t,J=7Hz,H-4), 2.95 (2H,q,
C19H3603 (312.48) J=15Hz,-CH 2-2)
MS, m/z: 408 (M-2H zO,30/0), 377 (15),350 (11),
Me-( CH2)12-CO-CHz-CH -COOH 333 (7), 323 (11), 235 (5), 221 (9), 184 (12), 153
I (4), 126 (6), 125 (15)
Me Deriv: Trimethyl 1,3,4-tricarboxy-3-hydroxy-
Crystals, mp 84 DC 19-oxoeicosanoate, mp 41-44 DC from the acid
MS, m/z 312 (M+), 281, 253, 211, 144, 129, 112 with CHzN z in acetone
StL: Cetraria islandica (L.) Ach. StL: Usnea meridensis Hale
Lit: Asahina and Shibata 1954; Solberg 1986 TLC: Rp 0.1 (silica gel, benzene: dioxane: AcOH
= 90:25 :4)
Lit: Keogh and Duran 1977
Linoleic acid (Linolensaure)
ClsH3Z0Z (280.44) (-)-2-Methylene-3(R)-carboxy-18(R)-
hydroxynonadecanoic acid [(-)-2-Methylen-
3{R)-carboxy-18(R)-hydroxynonadecansaurel
C21 H 3SOS (370.51)
Oil, mp -5 DC, bp16 229-230 DC, nbo 1.4711 20 1
Deriv: Linoleic acid tetrabromide, crystals (di- H2CYC02H
ethyl ether-pentane), mp 114-115 DC, by bromi- OH 2
, 3
nation of linoleic acid '~H3- f~ (CH2)14~~62H
StL: Evernia prunastri (1:) Ach., Peltigera
H
canina (L.) Willd.
Lit: Solberg 1975b Plates (AcOH-H 20), mp 83-84 DC, [am - 10
(MeOH, c 1.50)
UV(MeOH): 211 nm (3.65)
Methy13,4-dicarboxy-3-hydroxy-19-
IR(KBr): 724,764,820,864, 956,980, 1006, 1034,
oxoeicosanoate (3,4-Dicarboxy-3-hydroxy-19-
1064, 1076, 1110, 1130, 1138, 1190, 1210, 1260,
oxoeicosansauremethylester)
1278, 1300, 142~ 1474, 1628, 1700, 2900, 296~
CZ3H400S (444.55) 3200cm-1
IH-NMR (60MHz,CDCI3): 1.04 (3H,d,J=7Hz, C-8: 24.7, C-9-C-19: 28.1-29.4, C-20: 25.6, C-
Me-19), 1.19 [28H,bs,-(CH2)14-]' 3.35 (1H,t, 21: 39.0
J=7.2Hz,H-3), 3.53 (1H,m,H-18), 5.45 (2H,bs, MS, m/z: 368 (M+,3%), 367 (4),366 (9),353 (38),
2x-COOH), 5.60, 6.13 (2H,d,J=lHz,=CH 2 ) 350 (29), 332 (16), 324 (82), 307 (17), 279 (43),
MS, m/z: 352 (M-H 20, 9%), 337 (44), 334 (43), 261 (17), 168 (24), 155 (72), 142 (41), 139 (19),
308 (62), 290 (51), 280 (66), 263 (58), 247 (38), 123 (21), 111 (21), 109 (21), 98 (40), 83 (55),57
235 (28), 233 (28),219 (31),207 (33), 191 (41), (55), 55 (100),45 (97),43 (67),41 (72)
181 (42), 177 (52), 168 (67), 163 (57), 150 (70), CD (MeOH): L1259 + 0.29, L1222 - 9.12, L1200 + 3.50
139 (56), 126 (100), 109 (70) (sh)
CD (MeOH): L1352 + 0.16, M~240 + 0.18, L1225 + Deriv: Isomurolic acid, mp lIS-116C (MeOH),
0.28, L1220 + 0.15 by heating of murolic acid in dimethyl-
Deriv: (-)-2-Methylene-3(R)-carboxy-18- formamide at 150C for 30 min
oxononadecanoic acid, needles (acetone), mp StL: Lecanora muralis (Schreb.) Rabenh.
63-65C, [am - 5.9 (MeOH), from the acid with TLC: RF 0.30 (silica gel Merck 60F 254,
Jones' reagent toluene: AcOH = 85: 15. A: 23, B': 27, C: 24
StL: Parmotrema xanthinum (Miill.Arg.) Hale, Lit: Huneck et al. 1979; Ghogomu and Bodo
Usnea aliphatica Hale 1982
MC: Fig. 61A,B
Lit: Keogh and Zurita 1977; Huneck and Snatzke
Muronic acid (Muronsaure)
1980
C21 H 34 0 S (366.48)
Murolic acid (Murolsaure)
C21 H 36 0 5 (368.25)
Ha
10
H0
8
2Crt
6
3
'4 0
2
1
Ha
0
Hb
21
OH
! 20 18 16 14 12 10
H02~dHb
8 3 2
19 17 15 13 11 9 7
CH3- ! ; . " 0 1 0 Crystals (acetone-H 20), mp 93-94C, [aW +

H 19 17 15 13 11 9 7 12.8 (MeOH, c 1.065), [am + 8.7 (CHCI3)
Plates (MeOH), mp 110-111C, [a]b4 + 5.1 IR (KBr): 702, 720, 820, 870, 964, 980,1022,1040,
(MeOH, c 1.11) 1050, 1070, 1090, 1100, 1124, 1160, 1196, 1210,
UV (MeOH): 216nm (3.74) 1250, 1290, 1310, 1410, 1432, 1464, 1650, 1-700,
IR (KBr): 660, 720, 820, 850, 864, 890, 930, 986, 1740,2890, 2950, 3100cm-1
990, 1024, 1060, 1074, 1100, 1128, 1170, 1188, IH-NMR (270MHz,CDCI3): 1.26 [22H,bs-
1208, 1220, 1250, 1292, 130~ 1350, 1404, 1436, (CH 2)11-]' 1.74 (2H,m,-CH 2-7), 2.15 (3H,s,Me-
1470, 1650, 1702, 1730,2900,2950, 3500cm-1 21),2.43 (2H,t,J=7.5Hz,-CH 2-19), 3.63 (1H,ddd,
IH-NMR (270MHz,CDCI3:CD 30D=2: 1): 1.15 J3,4=6Hz,J3,S=3Hz,H-3), 4.81 (1H,ddd,J4,3=6Hz,
(3H,d,J=6.25Hz,Me-21), 1.28 [24H, bs, -(CHz}12-]' J4 ,j=6Hz,H-4), 6.02 (1H,d,Js,3=3Hz,H a-5), 6.46
3.61 (1H,ddd,J 3,4=6Hz,J3,S=3Hz,H-3), 3.74 (1H, (1 H,d,J s,3=3 Hz,Hb-5)
sextet,H-18), 4.83 (1H,dt,J 4,3=6Hz,J4,j=6Hz, 13C-NMR (20MHz,CDCI3):C-1: 173.5, C-2:
H-4), 6.02 (lH,d,Js,3=3Hz,H a-5), 6.37 (1H,d,Js,3= 133.1, C-3: 50.0, C-4: 79.2, C-5: 125.6, C-6:
3Hz,Hb-5) 168.5, C-7: 35.8, C-8: 24.8, C-9-C-17: 29.2-
13C-NMR (CDCI3): C-1: 173.3, C-2: 133.3, C-3: 29.4, C-18: 24.0, C-19: 44.0, C-20: 210.3, C-21:
125.5, C-4: 79.3, C-5: 68.7, C-6: 168.7, C-7: 35.7, 29.1
MS, m/z: 366 (M+,23%), 349 (8), 348 (28), 308 StL: Lecanora muralis (Schreb.) Rabenh.
(21),306 (10), 291 (5),290 (10),253 (15),251 (8), TLC: A: 30, B': 29, C: 29
239 (15), 225 (18), 211 (13), 193 (10), 155 (35), MC: Fig. 61C
142 (8),141 (8), 123 (8), 111 (8),109 (10), 97 (18), Lit: Huneck et aL 1979
95 (20),89 (10), 87 (23), 85 (18),71 (25),69 (35),
58 (38), 55 (50), 43 (100)
Nephromopsic acid (Nephromopssaure)
TLC: Rp 0.36 (silica gel Merck 60 F 254, toluene: C19H3404 (326.46)
AcOH = 85: 15)
Lit: Ghogomu and Bodo 1982
19
Neodihydromurolic acid Me
(N eodihydromurolsaure)
Leaflets (EtOH), mp 137C, laW - 85.1 (CHCI3)
C21 H 3SOS (370.51)
IR (KBr): 695, 980, 1010, 1180, 1200, 1245, 1330,
1355,1415,1465,1740 (lactone-CO), 2840, 2910,
OH 2950,2980,3030,3450 (COOH)
21 16 14 12
CH 3 IH-NMR (250MHz,CDCI3): 0.90 (3H,t,J=7Hz,
H 19 17 15 13 11 Me-19), 1.29 [22H,bs,-(CH2)1l-]' 1.38 (3H,d,
J=7Hz,Me-5), 1.58 (2H,m,-CH 2-7), 3.04 (IH,dq,
Plates (MeOH), mp 122-123C, laW + 17.1
J=10.7Hz,H-2), 3.22 (lH,dd,J=10a.8.5Hz,H-3),
(MeOH, c 1.59)
4.70 (lH,m,H-4), 5.50 (IH,bs,-COOH)
IR (KBr): 680, 702, 722, 784, 812, 850, 900, 932,
13C-NMR (63MHz,CDCIJ: 14.02, 14.39, 22.62-
970, 988, 1024, 1052, 1088, 1102, 1130, 1140,
31.86, 36.44, 51.56, 77.31, 175.00, 177.34. MS,
1158, 1200, 1258, 1316, 1366, 1386, 1402, 1430,
m/z 326 (M+,6%), 117 (40), 99 (26),56 (33), 55
1474,1708,1740,2900,2950,3500cm-1
(84), 44 (54),43 (100)
IH-NMR (270MHz,CDCI3:CD 30D = 9: 1): 1.16
Deriv: Methyl nephromopsate, leaflets (MeOH),
(3H,d,J=6Hz,Me-21), 1.27 [24H,bs,-(CH 2)12-]'
mp 60-61 c, from the acid with CH 2N2 in Et 20
1.33 (3H,d,J=6.4Hz,Me-5), 1.70 (2H,m,-CH 2-
StL: Nephromopsis stracheyi (Bab.) Mull.Arg.
19), 2.66 (lH,dd, h2=11Hz,J3,4=9Hz,H-3), 2.99
Lit: Mulzer et aL 1991
(lH,m,H-2), 4.50 (lH,ddd,J4,3=8Hz,J4,7=4Hz,
H-4)
MS, m/z: 370 (6%), 355 (60),352 (30), 334 (48), Nephrosteranic acid (Nephrosteransaure)
327 (64), 326 (l00), 308 (55),306 (38), 292 (44),
282 (66), 281 (98), 280 (65),278 (53), 264 (46), C17H3004 (298.41)
263 (46), 253 (65), 235 (55), '221 (60), 220 (74),
194 (51), 179 (46), 178 (48), 165 (41), 154 (51),
143 (51), 138 (55), 137 (60), 136 (41), 135 (60),
132 (86), 124 (62), 123 (77), 121 (65), 115 (60),
114 (74),111 (74),110 (78), 109 (90),97 (87),96 Plates (n-hexane), mp 95C, laW - 38.4 (CHCI3)
(92), 85 (96), 81 (92) IR (KBrJ: 670, 698, 720, 816, 890, 930, 976, 980,
Deriv: Methyl neodihydromurolate, mp 44- 1008, 1030, 1048, 1098, 1120, 1140, 1166, 1198,
44.5C (MeOH), [a]54 + 17.3 (MeOH), from 1250, 1310, 1358, 1380, 1398, 1420, 1432, 1468,
neodihydromurolic acid with CH2N2 1710, 1738,2890,2960,3200, 3500cm-1
IH-NMR (270Mz,CDCU: 0.88 (3H,t,J;:::6Hz,Me- !3C-NMR (20.1 MHz,CDCI3): C-l: 172.5, C-2:
17), 1.26 [18H,bs,-(CH2)9]' 1.37 (3H,d,J=8Hz, 138.5, C-3: 146.9, C-4: 81.0, C-5: 10.4, C-6:
Me-5), 1.72 (2H,m,-CH 2-7), 2.71 (IH,dd,J3,2 164.5, C-7: 32.1, C-8: 24.0, C-9-C-17: 28.4, 28.9,
=I1.5Hz,J3,4=9Hz,H-3), 2.99 (1H,m,H-2), 4.48 C-18: 25.1, C-19: 38.6, C-20: 68.4, C-21: 22.8
(IH,ddd,J4,3=8Hz,J4,7=4Hz,H-4) MS, m/z 368 (M+,2%), 367 (1), 366 (3), 353 (3),
StL: Nephromopsis endocrocea (Asah.) Lai 351 (5), 350 (21), 332 (5), 325 (9), 324 (30), 309
MC: Figs. 61D,62A (5), 306 (11), 280 (24), 279 (42), 207 (4), 206 (4),
Lit: Huneck et al. 1979 155 (27), 142 (21), 141 (6), 124 (6), 123 (9), III
(18), 109 (15), 55 (100)
Nephrosterinic acid (Nephrosterinsaure)
TLC: RF 0.35 (silica gel Merck 60 F 254, AcOH:
C17H 2S 0 4 (296.39) toluene = 85: 15. A: 31, B': 27, C: 29
Lit: Bodo and Molho 1980
HOOCtlH 6
3
Ha
2 b Norcaperatic acid (Norcaperatsaure)
17
Me~"'401 0
7 C2oH3607 (388.49)
Leaflets (acetic acid-water), mp 96C, [a]D + C02H
10.8 (CHCI3); mp of the racemate 83.5-84.5C n-C14H29tH
IH-NMR (60MHz,CDCI3): 0.88 (3H,t,Me-17), HO C0 2H
1.28 [20H,bs,-(CH2)1O-]' 3.65 (1H,m,H-3), 4.8 H H
(1H,m,H-4), 6.0 (1H,d,J=2.7Hz,H a-5), 6.49 (1H, C02H
d,J=2.8Hz,H b-5), 9.5 (1H,s,-COOH)
StL: Nephromopsis endocrocea (Asah.) Lai Crystals, mp 137-139C, [am - 16.0 (EtOH, c
Lit: Carlson and Oyler 1976; Huneck et al. 1979 0.19)
IR (KBr): 1706cm-1
Deriv: Dimethyl caperatate, needles (MeOH),
Neuropogolic acid (Neuropogolsaure) mp 56.5-57.5C, from norcaperatic acid with
C21H360S (368.25) CH 2 N 2
StL: Melanelia stygia (1.) Essl.
Lit: Mishchenko et al. 1984
Norrangiformic acid (Norrangiformsaure)

C2oH3606 (372.49)
Crystals (acetone-water), mp Ill-l12 DC, [am +
22.4 (CHCI 3) 2 H 19
IR (KBr): 710, 720, 770, 890, 1220, 1430, 1475, 1 /'1"C02H
H0 2C" 3' .. '
1665, 1705, 1740,2850,2920, 3420cm- 1
IH-NMR (80MHz,CDCI3): 1.20 (3H,d,Me-21), 4 20
n-C 14H29 : C0 2H
1.29 [22H,bs,-(CHz}1l-]' 1.52 (2H,m,-CH 2-),
H
2.03 (2H,m-CH 2-), 2.20 (3H,d,J=1.7Hz,Me-5),
3.31 (2H,s,-OH,-COOH), 3.81 (1H,m,H-20), Crystals, mp ll4-122 DC, [am + 12.9, [aJi,4 + 7.5
5.10 (1H,m,H-4) (MeOH)
IR (KBr): 670, 716, 734, 764, 792, 848, 882, 924, Waxy crystals, mp 63-64 DC, bplS 215 DC
1020, 1126, 1176, 1212, 1230, 1270, 1402, 1470, StL: Evernia prunastri (1.) Ach.
1670, 1700, 2850, 2930, 3150cm-1 Lit: Gavin and Tabacchi 1975
MS, m/z: 354 (M-H 20,54%), 336 (73), 318 (38),
308 (77), 290 (75), 280 (84), 264 (70), 252 (57),
Pentadecanoic acid (Pentadecansaure)
238 (49),220 (61),214 (67),210 (61), 200 (81),
196 (87), 186 (80), 182 (98), 168 (96), 154 (91), ClsH3002 (242.39)
140 (95), 126 (86), 112 (93), 98 (100), 84 (95)
Deriv: Methyl rangiformate, mp 48-49 DC CH3-(CHz)13-C02H
(MeOH), [aW + 9.6 (CHCI3), by methylation of Plates (acetone-HzO), mp 53 DC
norrangiformic acid with CH 2N z StL: Evernia prunastri (1.) Ach.
StL: Cladonia mitis Sandst. Lit: Gavin and Tabacchi 1975
TLC: B': 36
MC: Fig. 15A
Lit: Huneck 1982 Praesorediosic acid (Praesorediossaure)
C21 H 34 0 6 (382.48)
Oenanthic acid, Heptanoic acid (bnanthsaure,
Heptansaure) HooU 6 5
e
C7H l4 0 2 (130.18)
HOOC
21
7
,l,o~o
CH 3-(CH2)s-C02H
Microcrystals (CHCI3-n-hexane), mp 139-
Oil, mp -9 DC, bpll 115-116C, nb1.4170
140.5C, [a]D + 22.7 (MeOH)
IR (Nujol): 1705, 1740cm-1
lH-NMR (300MHz,CD 30D): 1.30 [24H,bs,-
(CH 2)12-]' 1.61 (2H,dt,J=7.0Hz,-CH2-), 2.14 (3H,
Oleic acid (blsaure) d,J=2.2Hz,Me-5), 2.29 (2H,t,]=7.2Hz,-CH2-20),
5.17 (1H,m,H-4)
ClsH3402 (282.45) MS, m/z 364 (M-H 20,1 %), 350 (0.4), 346 (0.4),
320 (0.5), 230 (1), 229 (2), 205 (1), 155 (1), 55
CH3-(CH2)7)c=CCH2)7-C02H (100); chern. ionization: 400 (M + NH 4,20%), 386
(11),384 (27), 383 (32),382 (M + NH 4-HP,100),
H H
381 (13), 370 (17), 369 (19),368 (55),367 (12),
Oil, bps 203-205 DC 366 (8), 365 (14),364 (8), 356 (14),351 (10),340
StL: Alectoria ochroleuca (Hoffm.) Mass., (14), 339 (32), 338 (79), 325 (18), 324 (41), 321
Evernia prunastri (1.) Ach. (12)
Lit: Gavin and Tabacchi 1975 ORD (MeOH): [a] 589: +23, 578: +24, 546: +27,
436: +42, 365 nm: +60
StL: Parmotrema praesorediosum (Nyl.) Hale
Palmitic acid (Palmitinsaure) TLC: A: 30, B: 39,C:35
Lit: David et al. 1990
Cl6H3202 (256.42)
CH3-(CH2)14-C02H
Protoconstipatic acid (Protoconstipatsaure) Lustrous plates (benzene or acetic acid, tem-

perature not above 50C), mp 107.5C, [albO +
C2lH360S (368.25)
12 (CHCI3) and - 12 (CHCI3) respectively
UV (MeOH): 218 nm (3.82)
IR (KBr): 715, 818, 865, 962, 975, 1020, 1100,
1120, 1170, 1190, 1210, 1250, BOO, 1350, 1400,
21
Me 1430, 1460, 1640, 1690, 1720, 2840, 2900, 3050,
H 3450cm-1
White flakes (benzene), mp 102-103C, [aHi' IH-NMR (270MHz,CDCI3:CD30D = 2: 1): 0.68
- 12 (CHCI3) (3H,t,J=6Hz,Me-19), 1.27 [22H,bs,-(CH2)1l-]'
1
IR (Nujol): 1710, 1743cm- (lactone-CO) 1.75 (2H,m,-CH 2-7), 3.60 (lH,ddd,J3,4=6H,J3,s=
IH-NMR (100MHz,acetone-d6): 1.10 (3H,d,J= 3Hz,H-3), 4.84 (lH,ddd,J4,3=6Hz,J4,7=6Hz,H-4),
6Hz,Me-21), 1.31 [26H,bs,-(CH 2)13-]' 3.77 (2H, 6.03 (lH,d,J=3Hz,H a-5), 6.39 (1H,d,J=3Hz,
m,H-3,H-20), 4.79 (1H,m,H-4), 6.00, 6.29 Hb-5).
(2H,m,=CH2-5) 13C-NMR (20Mz,CDCI3): C-1: 174.4, C-2: 132.6,
MS, m/z: 368 (M+,3%), 353 (24), 351 (11), 350 C-3: 49.6, C-4: 78.9, C-5: 125.9, C-6: 168.2, C-7:
(41),332 (10), 325 (18),324 (63), 306 (16),305 35.8, C-8: 24.8, C-9-C-17: 29.2, 29.4, C-18: 22.7,
(11),280 (26),279 (100),261 (11), 179 (12), 167 C-19: 14.0.
(12), 165 (14), 155 (45), 142 (43), 141 (12), 139 MS, m/z 324 (M+,10%), 296 (35), 279 (10), 251
(12), 137 (10), 122 (14), 121 (20), 111 (19), 109 (50), 155 (36), 142 (30), 57 (70),43 (100)
(16),97 (32), 96 (14),95 (32), 85 (13),83 (43),82 CD (in MeOH): Ll257 + 0.32, Ll22o - 9.62
(14),81 (29),71 (21),70 (15),69 (69),68 (16),67 Deriv: Addition product of CH2N2 to (-)-
(39),57 (41), 56 (20), 55 (97),45 (78),43 (39),41 protolichesterinic acid: prisms (MeOH) of mp
(61) 61C, [am - 288 (CHCI3), by treatment of (-)-
StL: Xanthoparmelia xanthosorediata (Elix) protolichesterinic acid with excessive CH2N2 at
Elix et Johnston room temperature for 4 h
TLC: RF 0.34 (silica gel, n-hexane: Et20: HCOOH StL: Cetraria ericetorum Opiz [(- )-protoliches-
= 13:8:2). A: 26, B': 17, C: 26 terinic acid)], Cetraria islandica (L.) Ach. [( +)-
Lit: Chester and Elix 1979b protolichesterinic acid]
TLC: A: 35, B: 47, B': 46, C: 37
MC: Fig. 15B
Protolichesterinic acid (Protolichesterinsaure) Lit: Martin et al. 1974; Carlson and Oyler 1976;
Cl9H3204 (324.45) Damon and Schlessinger 1976; Huneck et al.
1979; Huneck and Takeda 1992; Murta et al.
6 Ha 1993
HP2CttH
19 18 16 14 12 10 8 3 2 b
CH~""a a Protopraesorediosic acid
4
3 17 15 13 11 9 7 1
(Protopraesorediossaure)
(+)
C21 H 3P6 (382.48)
H
6 5
HaaC~CH2
.(4l~i-
21
( -) HaaC a1a
Microcrystals (CHCI 3-n-hexane), mp 123- IR (KBr): 714, 726, 842, 900, 966, 1006, 1120,
124C, [al D + 9.1 (MeOH) 1170, 1210, 1270, 1372, 1410, 1438, 1468, 1688,
IR (Nujol): 17l5, 1748cm-1 1722, 2940, 3200 cm- 1
IH-NMR (300MHz,CDCI3): 1.28-1.32 [24H,bs,- MS, m/z: 368 (M-HzO,24%), 350 (14), 336 (27),
(CH z)12-]' 1.67 (2H,m,-CHz-), 2.41 (2H,t,J= 322 (70), 308 (35), 290 (51), 280 (32), 264 (35),
7.2Hz,-CH z-20), 3.63 (1H,ddd,J=3 and 6Hz,H- 228 (35), 214 (66), 210 (45),200 (68), 196 (73),
3), 4.82 (1H,dt,J=6.0 and 6.1Hz,H-4), 6.02, 6.46 182 (100), 168 (86), 154 (86),140 (70), 132 (41),
(2H,2xd,=CH z-5) 126 (70), 112 (61),98 (84), 84 (66)
MS, m/z 364 (M - H 20,8%), 350 (0.9), 346 (2), Deriv: Dimethyl rangiformate, needles (MeOH),
320 (1),318 (1), 223 (2),209 (1), 205 (1), 155 (9), mp 48-49C, [an4+ 9.6 (CHCIJ, by methylation
55 (100); chern. ionization: 400 (M + NH 4,74%), of rangiformic acid with CHzNz
386 (10), 384 (17), 383 (21),382 (75), 381 (5),368 StL: Cladonia rangiformis Hoffm.
(11), 358 (9), 357 (14), 356 (68), 342 (10), 340 MC: Fig. 15D
(17), 339 (36), 338 (100), 325 (6), 324 (16), 323 Lit: Akermark 1967; Huneck and Steglich 1983
(8)
ORD (MeOH): [al 589: +9,578: +10, 546: +10,
Roccellaric acid (Roccellarsaure)
436: + 10, 365 nm: -2
StL: Parmotrema praesorediosum (Nyl.) Hale Cl9H3404 (326.46)
TLC: A: 26, B: 32,C:31
Lit: David et al. 1990 6 5
HOO~tire
19
Pseudonorrangiformic acid Me~"4010
(Pseudonorrangiformsaure) 7
C2oH3606 (372.49) Prisms (MeOH), mp 110-111 C, [an + 35

(CHCI3, c 1.73)
Structure unknown IR (KBr): 670, 700, 720, 760, 790, 818, 900, 950,
980, 1020, 1050, 1100, 1125, 1140, 1170, 1200,
Crystals, mp 189C (dec.), [am + 1.5
1250, 1320, 1360, 1380, 1400, 1430, 1472, 1710,
StL: Cladonia submitis Evans
1740, 2900, 3000, 3500 cm- 1
MC: Fig. 15C
IH-NMR (270MHz,CDCI3:CD 30D = 1: 1): 0.89
(3H,t,J=6Hz,Me-19), 1.27 [22H,bs,-(CH z)n-]'
1.33 (3H,d,J=8Hz,Me-5), 1.70 (2H,m,-(CH 2 )-7),
Rangiformic acid (Rangiformsaure) 2.68 (1H,dd,J3,z=I1.5Hz,J3,4=9.5Hz,H-3), 3.00
(IH,m,H-2), 4.50 (1H,ddd,J4,3=8Hz,J4,s=4Hz,H-
C21 H 3s 0 6 (386.51) 4)
MS, m/z 326 (M-, 100%), 325, 308, 281, 253,
193, 114
Deriv: Methyl roccellarate, needles (MeOH), mp
40-41C, [aH? + 25 (CHCI3), from roccellaric
acid witll ethereal CH 2N 2
StL: Roccellaria mollis (Hampe) Zahlbr.
MC: Fig. 16B
Needles (MeOH-H 20), mp 104-105C, [am + Lit: Huneck and Follmann 196h.Mulzer et al.
14.2 (EtOH) 1993
Roccellic acid (Roccellsaure) Crystals (EtOH), mp 156.4 C

StL: Peltigera canina (L.) Willd.
C17H 3P4 (300.43)
Lit: Solberg 1975b
110 H 1
H3c.i lC0 2H
Stearic acid (Stearinsaure)
15 ~ .. 17 ClsH3602 (284.47)
H 3 C-(CH 2l 1,..... C0 2H
H
CH3-( CH2) 16-C02H
Prisms (MeOH), mp l30C, [anD + 18 (EtOH, c
1.94) Leaflets (EtOH), mp 69.4,71-72 C
IR (KBr): 710,720,790,830,860,950,1200,1242, Deriv: Methyl stearate, mp 38-39C, from
1270, l380, 1420, 1460, 1700, 2580, 2680, 2900, stearic acid with CH2N2
3000cm-1 StL: Evernia prunastri (L.) Ach.
MS, m/z 300 (M+,12%), 282 (60), 264 (65), 254 Lit: Gavin and Tabacchi 1975
(25),237 (20),227 (30), 210 (25), 170 (60), 156
(70), 132 (72), 114 (92), 97 (100)
Tetrahydroxyfatty acids
Deriv: Dimethyl roccellate, mp 28.5-30.5C,
(Tetrahydroxyfettsauren)
from roccellic acid with ethereal CH2N2; [anD +
14.5 (CHCI3) C22H4406 (404.57) (x = 8, Y = 7)
IH-NMR (500MHz,CDCl3 ): 0.88 (3H,t,J=7.1Hz,
Me-IS), 1.l3 (3H,d,J=6.7Hz,Me-16), 2.65-2.73 Me-(CH,)x-CH-CH-CH,-CH-CH-(CH,)y-COOH
(2H,m,H-2,H-3), 3.69, 3.70 (2x 3H;, 2x s, 2x I I I I
OH OH OH OH
COOMe)
x = 6 -10, Y = 7 - 10
13C-NMR (125.6MHz,CDCIJ: 14.14 (Me-IS),
15.11 (Me-16), 22.75, 27.52, 29.43, 29.46, 29.61, White amorphous powder (dioxane or AcOH),
29.69, 29.74, 30.73, 32.00 (l1x -CH2-), 42.11 mp 178-194C
(CH), 48.62 (CH), 51.49, 51.73 (2x COOMe), IR (KBr): 720,945, 1060, 1280, 1445, 1470, 1700,
174.65, 175.31 (2x -.GOOMe) 3000, 3350 cm-1
StL: Leproloma membranaceum (Dickson) StL: Ophioparma ventosa (L.) Norman,
Vain., Roccella phycopsis (Ach.) Ach. Stereocaulon vesuvianum Pers.
TLC:A: 42,B: 60, C:48 Lit: c.P. Culberson 1969; Solberg 1977
MC: Pig. 16A
Lit: Huneck et al. 1994c Concerning further fatty acids and lipids from
lichens see:
Sativic acid, 9,1O,12,13-tetrahydroxystearic
1. Lipids: Dembitsky 1992
acid (Sativsaure, 9,1O,12,l3-
2. Patty acids: Solberg 1987, Dembitsky et al.
Tetrahydroxystearinsaure)
1991a,b, 1992a,b,c
C1sH 3P4 (348.47) 3. Phospholipides: Dembitsky et al. 1991a, 1993
4. Diacylglyceryltrimethylhomoserines: Dem-
13 12 10 9 1
Ml>-(CH 2 )4-CH-CH-CH2-CH-CH-(CH2 )7- COOH bitskyet al. 1993
I I I I 5. C40-C 130 polyisoprenoid alcohols: Rezanka
OH OH OH OH and Dembitsky 1993
3.7 Aromatic Compounds 155
3.7 Chloroatranol (Chloratranol)

Aromatic Compounds CsH 7CI0 3 (186.58)
3.7.1
Monocyclic Aromatic Compounds CI~
Atranol HOOH
CHO
Orange-yellow crystals (acetone or HP), mp
))
139-140.5C
React: FeCl3 dark olive-green, PD yellow
IR (KBr): 750, 825, 1095, 1182, 1205, 1288, 1460,
HOYOH
1644, 3430cm-1
CHO
IH-NMR (90MHz,CDCI3): 2.31 (3H,s,Me), 6.32
Faint yellow needles (H 20), mp 124C (1H,s,arom.-H), 6.40 (lH,s,-OH), 10.20 (IH,s,-
React: FeCl3 greenish black, on dilution olive CHO), 11.08 (1H,s,-OH)
green, PD yellow MS, m/z 186 (M+,87%), 185 (100), 168 (5), 140
UV (MeOH): 225, 282, 350 nm (13), 121 (3)
IR (KBr): 835,1038,1080,1205,1274,1304, 1354, StL: Evernia prunastri (L.) Ach.
1450, 1590, 1632, 3150cm-1 Lit: Koller and Popl 1934a,b; Gavin and
IH-NMR (60MHz,acetone-d6 ): 2.23 (3H,s,Me), Tabacchi 1975
6.25 (2H,s,2xarom.H), 10.27 (1H,s,-CHO), 10.68
(2H,bs,2x-OH)
MS, m/z 152 (M+,86%), 151 (100), 134 (6), 95 4,6-Dihydroxy-2-methoxy-3-
(10), 78 (6), 77 (15), 76 (4), 57 (16), 55 (10),51 methylacetophenone (4,6-Dihydroxy-2-
(16), 43 (26), 41 (27) methoxy-3-methylacetophenon)
Deriv: Atranoloxime, brownish leaflets, mp ClO H 12 0 4 (196.20)
188-190C (dec.), from atranol with hydroxyl-
amme CH 3
StL: Evernia prunastri (L.) Ach., Stereocaulon H 0 ' 0 0CH3
vesuvianum Pers. YCO-CH3
Lit: pfau 1933; Whalley 1949; Gavin and OH
Tabacchi 1975; Caccamese et al. 1986
Crystals (benzene), mp 143-144C
UV (EtOH): 231 (4.32),247 (4.21), 305nm (3.64)
Benzoic acid (Benzoesaure) IR (KBr): 1656,3350, 3700cm-1
C7H 6 0 2 (122.11) IH-NMR (60MHz,CDCI3 ): 2.10 (3H,s,Me-), 2.44
(3H,s,-CO-Me), 3.90 (3H,s,-OMe), 6.19 (1H,s,
arom.-H), 5.19, 11.98 (2xIH,2xs,2x-OH)
MS, mh 196 (M+,66%), 165 (98), 136 (100)
StL: Stereocaulon vesuvianum Pers.
Crystals, mp 122C Lit: Bolognese et al. 1974
StL: Letharia vulpina (L.) Hue
Lit: Bachelor and Cheriyan 1976
1
5,7-Dihydroxy-6-methylphtalide 3'
(5,7 -Dihydroxy-6-methylphthalid) Me
C9H s04 (180.15)
l'
6 12 eOOH
HO 4 OH
3
Prisms (HC0 2Et-CHCI3), mp 157-159, 179C
(acetone-HzO)
React: NaOCI red, FeCl3 (EtOH) violet
OH IR (KBr): 630, 800, 1240, 1280, 1465, 1580, 1615,
1630,2880,2960, 3380cm-1
MS, m/z 180, 162 IH-NMR (100MHz,CDCI3 ): 0.93 (3H,t,J=7Hz,
StL: Anamylopsora pulcherrima (Vain.) Timdal Me-3'), 1.67 (2H,m,-CH z-2'), 2.97 (2H,t,J=
TLC: A: 43, B': 25, C: 15, E: 11, G: 43 8Hz,-CH z-1'), 6,30 (1H,d,J=2.5Hz,H-3), 6.37
HPLC: RI-3 (1H,d,J=2.5Hz,H-5), 9.60 (3H,bs,2x-OH,-
Lit: Huneck and Elix 1993 COOH)
MS, m/z 196 (M+,37%), 178 (100), 150 (19), 121
l,l-Dimethylnoneicosyl everninate (34)
(Everninsaure-1, 1-dimethylnoneicosylester) Deriv: Methyl divarate, mp 78C (n-hexane),
from divaric acid with the calculated amount of
C41H7404 (631.00) CH 2N2 in EtzO at OC
StL: Protousnea malacea (Stirt.) Krog
ti
CH CH 3 Lit: Hesse 1911; Sonn 1928b; Asahina and Akagi
3 I
COO- c-n- C29H59 1935; Harris and Carney 1967; Durrani and
I I
Tyman 1980; Chamy et al. 1985; Dyke et al. 1987
CH 0 ~ OH CH3
3
Crystals (MeOH), mp 60C Divarinol

IR (KBr): 1000-1040, 1150, 1190-1220, 1260, C9H!2 0 2 (152.19)
1320, 1450, 1575, 1650 cm- 1 3'
lH-NMR (200MHz,DMSO-d 6): 0.90 (3H,t,Me),
~
1.00 [6H,s,-C(Me)2-], 2.50 (3H,s,arom.Me), 3.80 ME' 11
(3H,s,-OMe), 5.90 (2H,s,2x arom.-H)
5
MS, m/z: 630 (1%), 603 (4), 602 (10), 575 (11),
574 (11), 546 (14), 183 (52), 166 (15), 165 (77), 3 1
164 (100),149 (12), 136 (36), 111 (13),97 (32), 87 HO OH
(19),83 (43),82 (16), 71 (43),69 (16),65 (13),57 Leaflets (HzO), mp 51C, anhydrous (from ben-
(71),55 (65),43 (68),41 (56) zene), mp 84C
StL: Evernia prunastri (1.) Ach. React: NaOCI red-violet, FeCl3 (EtOH) violet
Lit: Nicollier 1979 UV (MeOH): 274nm (3.21)
IR (KBr): 1470, 1600,2950, 3600cm-1
IH-NMR (CDCl3 ): 0.91 (3H,t,J=7.5Hz,-Me), 1.57
Divaric acid (Divarsaure)
(2H,m,-CH z-2'), 2.45 (2H,t,J=7.5Hz,-CH 2-1'),
ClOH!204 (196.20) 6.18 (1H,bs,H-2), 6.24 (2H,bs,H-4,H-6)
13C-NMR (CDCI3 ): C-1': 37.9, C-2': 24.1, C-3': 3'
ii
13.8
MS, m/z 152
Deriv: Diacetyldivarinol, mp 12-15C, from
SMe11 1 COOC 2HS
divarinol with ACzO-HzS04
StL: Evernia prunastri (1.) Ach. Me-O OH
Lit: Mauthner 1924; Sonn 1931b; Asahina 1936; 3
Gavin and Tabacchi 1975; Kinoshita et al. 1994 Needles (n-hexane), mp 41-42 C
IR (KBr): 710, 1160, 1250, 1460,1580,1615,1650,
Divarinolmonomethylether 2880, 2960, 3400 cm- 1
lH-NMR (100MHz,CDCI3 ): 0.97 (3H,t,J=7Hz,-
ClOH 140 Z (166.21) Me), 1.43 (3H,t,J=8Hz,-O-CHz-Me), 1.67 (2H,
b
m,-CHz-Me), 2.90 (2H,t,J=8Hz,benzyl.-CHz-),
3' 3.80 (3H,s,-OMe), 4.43 (2H,q,J=8Hz,-O-CH z-
M Me), 6.63 (1H,d,J=3Hz,H-3), 6.70 (lH,d,J=3Hz,
;
H-5), 11.90 (lH,s,-OH)
5 " MS, m/z 238 (M+,40%), 193 (35), 192 (100), 177
3 , (9),164 (35), 135 (41)
MeO OH StL: Protusnea malacea (Stirt.) Krog
Lit: Sonn 1931b; Chamy et al. 1985
Oil
UV (MeOH): 273 nm (3.20)
IR (film): 704, 792, 844, 950, 990, 1058, 1092, Ethyl everninate (Everninsaureethylester)
1150, 1192, 1230, 1348, 1468, 1500, 1600, 2960, Cll H l4 0 4 (210.22)
3450cm-1
lH-NMR (60MHz,CDCI3 ): 0.78 (3H,t,J=6.5Hz,
Me-), 1.11-1.76 (2H,m,-CH z-Me), 2.34 (2H,t,
J=6.5Hz,benzyl.-CH z-), 3.58 (3H,s,-OMe), 5.30
(1H,bs,-OH), 6.06, 6.12 (2H,2xd,J=1.5Hz,H-
4,H-6), 6.08 (1H,s,H-2)
13C-NMR (CDCI3 ): C-1: 163.1, C-2: 98.8, C-3: Prisms (EtOH), mp 73-74C, needles (EtOAc-
156.4, C-4: 107.6, C-5: 146.5, C-6: 106.3, C-1': n-hexane), mp 74-77C
38.1, C-2': 24.2, C-3': 13.8, -OMe: 55.2 React: FeCl3 blue
StL: Evernia prunastri (1.) Ach. lH-NMR (270MHz,CDCI3 ): 1.41 (3H,t,J=7.3Hz,
Lit: Gavin and Tabacchi 1975; Kinoshita et al. -O-CHz-Me), 2.51 (3H,s,-Me), 3.80 (3H,s,-
1994 OMe), 4.39 (2H,q,J=7.3Hz,-O-CH z-), 6.28 (1H,
d,J=2.4Hz,H-3), 6.32 (lH,d,J=2.4Hz,H-5), 11.85
(1H,s,-OH)
Ethyl divaricatinate StL: Evernia prunastri (1.) Ach.
(Divaricatinsaureethylester) Lit: Walbaum and Rosenthal 1924; Aghoramurthy
C13 H 1S 0 4 (238.27) and Seshadri 1952; Cleaver et al. 1976; Gavin and
Tabacchi 1975; Jiang 1991
Ethyl haematommate -CH2-Me), 1.52 (2H,m,Ar-CH 2-CH 2-), 2.85

(Haematommsaureethylester) (2H,t,J=7.5Hz, Ar-CH 2-), 6.28, 6.33 (2H,2xd,
J=2Hz,H-3,H-5), 3.80 (3H,s,-OMe), 4040 (2H,q,
CllH120s (224.21)
*
J=7.3Hz,-0-CH 2-Me), 11.86 (1H,s,-OH)
Me StL: Cladonia macaronesica Ahti, Icmadophila
1 COOC2H5 ericetorum (1.) Zahlbr.
Lit: Solberg 1977; Gonzalez et al. 1991
HO 3 OH
CHO Ethyl orsellinate (Orsellinsaureethylester)
Crystals (MeOH-H 20), mp 113C CIOH i2 0 4 (196.20)
React: NaOCI red, PD yellow
IR (KBr): 450, 540, 570, 620, 730, 810, 860, 900, Me
1020, 1110, 1120, 1180, 1220, 1260, 1320, 1375, 5~COOC2H5
139~ 1410, 146~ 1560, 1610, 1650, 3000,
3400cm-1 HO~OH
lH-NMR (200MHz,CDCI3 ): 1.43 (3H,t,-CH 2-
Me), 2.53 (3H,s,-Me), 4042 (2H,q,J=4Hz,-CH 2-), Prisms (MeOH-H 20), mp 131-132C
6.28 (1H,s,arom.-H), 10.32 (lH,s,-CHO), 10040, React: NaOCI red
10.98 (2H,2xs,2x-OH) UV (EtOH): 219 (4.27),265 (4.11), 302nm (3.71)
MS, mlz 224 (M+,16%), 195 (11), 179 (9), 178 IR (KBr): 700, 894, 1062, 1178, 1270, 1320, 1368,
(15), 177 (12), 151 (12), 150 (100), 149 (7), 122 1380, 1405, 1447, 1470, 1478, 1500, 1585, 1640,
(24),121 (10),94 (20), 93 (14), 69 (15), 66 (22),65 3360, 3420 cm- 1
(22),53 (23),51 (16),39 (22), 28 (19) lH-NMR (60MHz,CDCI3 ): 1.42 (3H,t,J=6.9Hz,-
StL: Pseudevernia furfuracea (1.) Zopf O-CH2-Me), 2.53 (3H,s,-Me), 4046 (2H,q,J=
Lit: pfau 1933; Cresp et al. 1973; Macmillan and 6.9Hz,-O-CH 2-Me), 6.36 (2H,s,H-3,H-5), 11.92
Browne 1977 (2H,s,2x-OH)
MS, mlz 196 (M+,35%), 167 (1), 151 (25), 150
(100), 122 (20),94 (5),69 (8)
EthyI4-0-methylolivetolcarboxylate
Deriv: Orsellinic acid, mp 197-198 c (acetone-
(4-0-Methylolivetolcarbonsaureethylester)
H 20), from ethyl orsellinate by hydrolysis with
C1sH 22 0 4 (266.33) N aOH -H 20 at room temperature
StL: Roccella fuciformis (1.) DC.
TLC:A:62,B:66,C:44
Lit: Sonn 1928a; Anker and Cook 1945; Marmor
1972; Gavin and Tabacchi 1975; Hase et al. 1978;
Bartlett et al. 1983; Dyke et al. 1987
Haematommic acid (Haematommsaure)

Oil C9HgOs (196.15)
IR (CHCI3 ): 1570, 1610, 1650, 3350cm-1
lH-NMR (CDCI3 ): 0.89 (3H,t,J=7Hz,-CH 2-Me),
1.30 (4H,m,-CH 2-CH2-), 1.41 (3H,t,J=7.3Hz,
*
9 m,-CH 2-2'), 2.60 (2H,t,J=7.5Hz,H-21'), 3.76,
ME?
3.85 (2x3H,2xs,2x-OMe), 6.28, 6.35 (2H,2xd,
6 1 ~OOH J=2.8Hz,2xarom.-H), 5.25 (1H,s,-OH)
4 2 I3C-NMR (50.32MHz,CDC13): C-1: 137.84, C-2:
HO 3 OH 146.94, C-3: 96.99, C-4: 153.02, C-5: 106.22, C-
CHO 6: 128.99, C-1': 32.10, C-2'-C-19': 29.52-30.21,
8 C-20': 22.85, C-21': 14.23, OMe: 55.99, 56.21
Needles (EtOH-H 2 0), mp 172-173C (dec.) MS, m/z 448 (M+,4%), 194 (2), 180 (8), 177 (4),
React: PD yellow 169 (9), 168 (100), 167 (98), 166 (7), 153 (37), 139
IR (KBr): 720, 746, 820, 846, 870, 1030, 1080, (62), 137 (33), 125 (24), 123 (15), 109 (20), 107
1124, 1176, 1206, 1250, 1284, 1364, 1380, 1420, (16), 97 (13), 95 (14)
1454, 1560, 1630, 3000 cm- l Deriv: Hierridin acetate, mp 50-52C (EtOH),
IH-NMR (200MHz,CDC13): 2.60 (3H,s,-Me), from hierridin with Ac 20 in pyridine at room
6.36 (1H,s,H-5), 10.35 (1H,s,-CHO), 12.55 temperature
(2H,bs,2x-OH) StL: Ramalina hierrensis Krog et 0sth.
I3C-NMR (25.05MHz,CDC13): C-1: 103.7, C-2: HPLC: R] 84
168.1, C-3: 108.3, C-4: 166.5, C-5: 112.0, C-6: Lit: Gonzalez et al. 1992a,b
152.2, C-7: 171.9, C-8: 193.7, C-9: 25.1
MS, m/z 196 (M+,50%), 178 (27), 152 (38), 151
3-Hydroxy-5-methyl-4,6-dimethoxy-2-(tricos-
(55), 150 (100), 122 (44), 121 (17), 86 (50), 84
9'-enyl)-benzene [3-H ydroxy-5-methyl-4,6-
(72), 51 (72), 49 (94), 48 (27), 47 (66)
dimethoxy-2-(tricos-9-enyl)-benzen]
Deriv: Methyl haematommate, needles (MeOH),
mp 146-147C (dec.), by methylation of hae- C32Hs603 (488.77)

matommic acid with the equivalent amount of
, '0' 9' "
CH 2N2 in Et20 at C Me0'6tlt(CH2)13-CH=CH-(CH2)7-Me
StL: Asahinea chrysantha (Tuck.) W. Culb.
et C. Culb., Pseudevernia furfuracea (1.) Me~OH
OMe
Zopf
Lit: pfau 1933; Macmillan and Browne 1977; Physical data not given
Stepanenko et al. 1985 StL: Letharia vulpina (1.) Hue
Lit: Tabacchi and Tsoupras 1987
Hierridin
C29Hs203 (448.29) 4-0-Methylolivetolcarboxylic acid
(4-0-Methylolivetolcarbonsaure)
OH
C I3 H 1s0 4 (238.27)
4
OMe
Crystals (EtOH), mp 70-72 C
IR (CHCU: 1150, 1200, 1375, 1430, 1460, 1490,
1600, 2840, 2920, 2990, 3540 cm- l
IH-NMR (200MHz,CDC13): 0.88 (3H,t,J=6Hz,
Me-I'), 1.28 (32H,m,-CH 2-3' -19'), 1.58 (4H,
Crystals, mp 123C MS, m/z 196 (M+,490/0), 165 (26), 162 (100), 137
IR (CHCI3): 1570, 1610, 1630, 2400-3300, (10),136 (99), 108 (10),107 (10), 83 (11),44 (48),
3480cm-1 43 (17)
IH-NMR (CDCI3 ): 0.91 (3H,t,J=6.9Hz,Me-5'), StL: Parmotrema tinctorum (Nyl.) Hale,
1.36 (4H,m,-CH 2-3',4'), 1.60 (2H,m,-CH 2-2'), Stereocaulon alpinum Laur., Stereocaulon
2.93 (2H,t,J=7.4Hz,-CH 2-1'), 3.82 (3H,s,-OMe), vesuvianum Pers.
6.35 (2H,s,H-3,H-5) TLC: A: 64, B: 70, C: 52
!3C-NMR (50.32MHz,CDCI3 ): C-l: 114.4, C-2: HPLC: RT 3.34 min
165.2, C-3: 99.0, C-4: 166.8, C-5: 103.5, C-6: Lit: Gavin and Tabacchi 1975; Hylands and
149.9, C-l': 36.8, C-2': 32.1, C-3': 31.5, C-4': Ingolfsdottir 1985; Caccamese et al. 1986;
22.6, C-5': 14.2 Kawahara et al. 1988
MS, m/z 238 (M+,260/0), 220 (33), 192 (25), 182
(39),177 (5), 164 (100), 137 (28)
Methyl orsellinate (Orsellinsauremethylester)
StL: Cladonia macaronesica Ahti
Lit: Gonzalez et al. 1991 C9H 1004 (182.17)
Methyl B-orcinolcarboxylate 8
(B-Orcincarbonsauremethylester) Me 7
~COOMe
C lO H l2 0 4 (196.20)
9 HO ~ OH
Me
5hloOMe Crystals (EtOAc-n-hexane), mp 138-139C,
needles (MeOH-H 20), mp 142C
HO~OH React: NaOCI red
Me UV (MeOH): 214, 262, 300nm
8 IH-NMR (CDCI3 ): 2.49 (3H,s,-Me), 3.92 (3H,s,-
Prisms (acetone or benzene), mp 140-141, 143- COOMe), 6.31 (2H,s,2xarom.-H), 11.77 (1H,s,-
144C OH)
React: NaOel orange, FeCl3 (EtOH) violet-black, 13C-NMR (15.04MHz,DMSO-d6): C-l: 107.0, C-
on dilution with EtOH olive green, on addition 2: 161.2, C-3: 100.4, C-4: 161.5, C-5: 110.3, C-6:
of H 2 0 violet 141.1, C-7: 170.3, C-8: 22.2, -COOMe: 51.6 .
UV: 267 (4.0), 299nm (3.4) MS, m/z 182 (M+'290/0), 150 (100), 122 (82), 94
IR (KBr): 734, 790, 810, 834, 950, 1000, 1038, (32), 69 (48), 52 (40)
1064, 1110, 1160, 1192, ~280, 1310, 1370, 1420, TLC: A: 54, B': 56, C: 37, E: 41
1442,1502, 1600, 1620,2950,3100, 3450cm-1 StL: Pseudocyphellaria crocata (1.) Vain.
IH-NMR (100MHz,CDCIJ: 2.10 (3H,s,Me-8), HPLC: RJ 5
2.45 (3H,s,Me-9), 3.92 (3H,s,-COOMe), 5.23 Lit: Maass 1975b; Griffin and Staunton 1975;
(IH,s,OH-4), 6.20 (1H,s,H-5), 12.04 (1H,s, Sargent et al. 1975; Dyke et al. 1987; Chiarello
OH-2) andJoullie 1988
13C-NMR (50.3MHz,CDCI3 ): C-l: 105.2, C-2:
158.0, C-3: 108.5, C-4: 163.1, C-5: 110.5, C-6:
(+)- Montagnetol
140.2, C-7: 172.6, C-8: 7.6, C-9: 24.1, -COOMe:
51.8 C12 H I6 0 7 (272.25)
1977; Jaxa-Chamiec et al. 1980; Girard et al.

1987; Gonzalez et al. 1991
Olivetolcarboxylic acid (Olivetolcarbonsaure)

C12H 16 0 4 (224.25)
Needles (MeOH), mp 136.5 DC, [a]D + 16 (H 20)
5'
React: FeCl3 dark purple, NaOCl dark red Me
UV (MeOH): 262 (3.9), 298nm (4.3)
MS, m/z 272 (M+,9%), 256 (5), 254 (5), 236 (7),
169 (5), 168 (9), 152 (6), 151 (52), 129 (8), 125 (8),
124 (36), 123 (26), 122 (20), 111 (10)
StL: Roccella montagnei Bel.
HPLC: Rj 2
Crystals (benzene), mp 145, 148-149 DC
React: NaOCl red-violet (fades soon), FeCl3
Olivetol (EtOH) brown-red
IR (KBr): 700, 730, 776, 808, 830, 870, 900, 980,
Cll H 16 0 2 (180.24)
1020, 1062, 1120, 1170, 1202, 1240, 1280, 1362,
1412, 1450, 1470, 1580, 1630, 2550, 2900, 3000,
5'
Me 3450cm-1 IR (film): 1590, 1600, 1630, 3200-
3500cm-1
IH-NMR (acetone-d6 ): 0.90 (3H,bt,-Me), 1.1-1.8
(6H,m,-CH 2-2' -4'), 2.95 (2H,bt,-CH 2-1'), 6.20,
6.28 (2x1H,2xd,H-3,H-5). IH-NMR (CD 30D):
0.91 (3H,t,J=6.4Hz,-Me-5'), 1.35 (4H,m,-CH 2-
HO OH 3',4'), 1.57 (2H,m,-CH 2-2'), 2.88 (2H,t,J=7.5Hz,-
2
CH 2-1'), 6.14, 6.19 (2x1H,2xd,J=2.0Hz,H-3,
Leaflets (S02-containing H 20), mp 40-41 DC, H-5)
prisms, mp 46 DC 13C-NMR (25.2MHz,acetone-d6): C-l: 104.2, C-
React: NaOCl red, FeCl3 (EtOH) green-brown 2: 167.2, C-3: 101.6, C-4: 163.4, C-5: 111.5, C-6:
UV (MeOH): 272 (3.37), 280nm (3.12) 149.8, C-7: 174.0, C-1': 37.0, C-2': 32.2, C-3':
IR (CHCl3 ): 1600, 1710, 1790, 3150cm-1 32.6, C-4': 22.9, C-5': 14.1
IH-NMR (200MHz,CDCl3 ): ,0.87 (3H,t,J=7.5Hz, MS, m/z 224 (M+,46%), 206 (45), 180 (66), 168
Me-5'), 1.20-1.40 (4H,m,-CH 2-3',4'), 1.45-1.65 (27), 150 (24), 124 (100)
(2H,m,-CH 2-2'), 2.47 (2H,t,J=7.5Hz,-CH2-1'), StL: Cladonia macaronesica Ahti
5.40 (2H,bs,2x-OH), 6.15-6.35 (3H,H-2,4,6) Lit: Asahina and Hiraiwa 1935; Asahina and
MS, m/z 180 (M+,71 %),165 (4),151 (5), 138 (27), Yasue 1937; Harris and Carney 1967; Durrani
137 (25), 125 (23), 124 (100),107 (5), 95 (9) and Ty~an 1980; Porwoll and Leete 1985; Dyke
StL: Cladonia macaronesica Ahti et al. 1987; Gonzalez et al. 1991
Lit: Asahina and Asano 1932; Korte and Sieper
1960; Baeckstrom and Sundstrom 1970;
Krishnamurty and Prasad 1975; Focella et al.
Olivetolmonomethylether MS, m/z 124 (M+,100%), 107, 94

StL: Evernia prunastri (1.) Ach., Roccella
C12 H,s02 (194.26)
montagnei Bel.
5' Lit: Gavin and Tabacchi 1975
M~
13-0rcinol
CSHlO02 (138.16)
OH
Oil
IR (CHCI3 ): 1590,1610, 3580cm-'
'H-NMR (CDCI 3 ): 0.89 (3H,t,J=6.3Hz,Me-5'),
1.32 (4H,m,-CH 2-3',4'), 1.58 (2H,m,-CH,-2'),
2.51 (2H,t,J=7.5Hz,-CH2-1'), 3.76 (3H,s,-OMe), Needles or prisms (H 20 or benzene), mp 158-
6.26, 6.29 (2xIH,2xd,J=1.3Hz,2arom.-H), 6.34 159, 163C
(IH,d,J=I.2Hz,arom.-H) React: NaOCI red, FeCI3 (H 20) greenish
13C-NMR (50.32MHz,CDCI3 ): C-1: 156.7, C-2: IR (KBr): 732, 768, 838, 936, 990, 1085, 1130,
98.9, C-3: 160.8, C-4: 106.9, C-5: 145.9, C-6: 1180, 1310, 1368, 1428, 1466, 1530, 1590, 1630,
108.2, C-l': 36.1, C-2': 31.6, C-3': 30.9, C-4': 3000, 3350 cm-'
22.6, C-5': 14.1 Deriv: Dibromo-l3-orcinol, mp lSI-152C
MS, m/z 194 (M+,21 %), 152 (13), 138 (100) (EtOH-H 20), by bromination of l3-orcinol with
StL: Cladonia macaronesica Ahti Br2 in CS2
Lit: Gonzalez et al. 1991 StL: Evernia prunastri (1.) Ach.
Lit: Whalley 1949; Gavin and Tabacchi 1975
Orcinol
13-0rcinolcarboxylic acid
C7H s02 (124.13)
(13-0rcinolcarbonsaure)
7
Me-
C9H lO 0 4 (182.17)
~5 3 9
*
HO OH
Needles (H 20), mp 106-108C
6M~ ~OOH
React: NaOCI red
IR (KBr): 690, 720, 835; 850, 980, 1035, 1155, HO 4 3 OH
1205, 1300, 1330, 1380, 1480, 1515, 1600, 1620, M~8
3350cm-'
'H-NMR (250MHz,acetone-d6 ): 2.14 (3H,s, Crystals (acetone-H 2 0), mp 184C
Me-), 6.15 (3H,s,3xarom.-H), 8.10 (2H,s,2x- React: NaOCI red, FeCl3 blue-violet
OH) uv .(MeOH): 217 (4.41), 266 (4.14), 303nm
13C-NMR (75.47 MHz,DMSO-d6 ): C-1: 139.19, (3.56)
C-2, C-6: 107.11, C-3,C-5: 158.25, C-4: 99.77, IR (KBr): 1097, 1190, 1266, 1490, 1596, 1612,
C-7: 21.24 1635, 3400 cm-'
IH-NMR (200MHz,CD 30D): 2.00 (3H,s;Me-), ~-Orcinolmonomethylether

2.47 (3H,s,Me-), 6.22 (1H,s,arom.-H)
C9H 12 0 2 (152.19)
13C-NMR (25.05MHz,CDCIJ: C-1: 105.4, C-2:
163.0, C-3: 108.8, C-4: 158.2, C-5: 110.7, C-6:
140.2, C-7: 171.5, C-8: 7.6, C-9: 23.9, -COOMe:
51.7
MS, m/z 182 (M+,52%), 165 (12), 164 (75), 163
(10), 137 (12), 136 (100), 135 (13), 108 (13), 107
(17),80 (9), 79 (16), 77 (16),67 (9), 65 (8),55 (9),
53 (14), 52 (8), 51 (10),43 (10) Crystals (benzene), mp 118-121 DC
StL: Pseudevernia furfuracea (1.) Zopf StL: Evernia prunastri (1.) Ach.
Lit: Takenaka et al. 1972; Gunzinger 1985 Lit: Gavin and Tabacchi 1975
Orcinoldimethylether Orsellinic acid (Orsellinsaure)

C9 H 12 0 2 (152.19) CSHS04 (168.14)
8
Me
~bOOH
HO 4 3 OH
Oil, bps 102 DC, n}i 1.52342
Needles (MeOH-H 20), mp 184-185 DC (dec.),
197-198 DC (dec.)
React: NaOCI red, FeCl3 purple-violet
Orcinolmonomethylether, 3-Hydroxy-5- UV: 212, 262, 300nm
methoxytoluene (3-Hydroxy-5- IR (KBr): 692, 730, 800, 846, 880, 1000, 1030,
methoxytoluen) 1060, 1170, 1220, 1280, 1310, 1360, 1464, 1506,
1630, 3050,3540, 3630 cm- 1
CSHlO02 (138.16) IH-NMR (270MHz,acetone-d6 ): 2.52 (3H,s,Me-
Me 8), 6.23 (1H,d,J=2.56Hz,H-3), 6.29 (1H,d,J='
2.56Hz,H-5), 12.00 (2H,bs,2x-OH)
MeO ~
5
.
3
OH
13C-NMR (15.04MHz,DMSO-d6 ): C-1: 105.0, C-
2: 161.8, C-3: 100.6, C-4: 164.5, C-5: 110.9, C-6:
142.9, C-7: 173.3, C-8: 23.5
Crystals (benzene-n-pentane), mp 63 DC MS, m/z 168 (M+), 150, 124, 122
IH-NMR (200MHz,CDCI3 ): 2.25 (3H,s,-Me), Deriv: Methyl orsellinate, needles (MeOH-H 20),
3.82 (3H, s,-OMe), 6.27, 6.30, 6.35 (3x1H, mp 142 DC, by methylation of orsellinic acid with
3xs,3xarom.-H) the equivalent amount of CH 2N 2 in Et 20 at -
MS, m/z 138 (M+,1000/0), 137 (9), 123 (6), 110 10 DC. Methyl di-O-methylorsellinate, needles
(28), 109 (28), 107 (27),95 (9) (benzene), mp 44-45 DC; by methylation of
StL: Evernia prunastri (1.) Ach. orsellinic acid with dimethyl sulphate-K2C0 3 in
Lit: Gavin and Tabacchi 1975 acetone. Diacetylorsellinic acid, mp 142 DC (ben-
zene), by acetylation of orsellinic acid with noldimethylether, 2-chloro-5-0-methylorcinol,

Ac20-pyridine and thymol (Gavin et al. 1978).
TLC: A: 37,B': 49, C: 22 3.8
HPLC: Rt 2.59 min, Rj -2 Quinones
Lit: Sonn 1928a; Kloss and Clayton 1965; Harris
and Carney 1967; Douglas and Money 1967; 3.S.1
Santesson 1970c; Gaucher and Shepherd 1971; Benzoquinones
Unverricht et aI. 1972; Maass 1975b, Durrani
and Tyman 1980; Jaxa-Chamiec et al. 1980; Dyke
et al. 1987
Phthalic acid (Phthalsaure)

CSH604 (166.12)
~COOH
Red needles (EtOH-H20), mp 127-128 DC
~COOH UV (EtOH): 228 (4.3), 259 (4.0), 317 (3.9),
Plates (H 20), mp 231, 191 DC (in a sealed tube) 453nm (2.9)
StL: Evernia prunastri (1.) Ach. IR (KBr): 1540, 1580, 1615, 1660 cm-1
Lit: Gavin and Tabacchi 1975 IH-NMR (90MHz,CDCI3 ): 2.42 (3H,bs,Me-1),
The following aromatic compounds have 4.01, 4.02 (2x3H,2xs,2x-OMe), 6.40 (lH,bs,
been detected by GLC in small amounts in H-3)
Evernia prunastri (1.) Ach.: benzene, toluene, l3C (22.5 MHz,CDCI3 ): 13.8, 61.4 (2 C), 104.3,
isopropylbenzene, m-ethyltoluene, mesitylene, 127.9, 145.5, 145.8, 148.4, 160.1, 171.5, 178.5
1,2,3-trimethylbenzene, isobutylbenzene, bro- MS, m/z 222 (M+,100%), 207 (92), 193 (41), 179
mobenzene, 1,2-dimethyl-3-ethylbenzene, 1- (58), 177 (73), 151 (56), 108 (45), 95 (44)
c~loro- 2,4-dimethoxy-6-methylbenzene, a, p- StL: Graphis desquamescens (Fee) Hale et Wirth
dlmethylstyrene, naphthalene, bis-(p-tolyl)- Lit: Miyagawa et al. 1994
1,2-ethane, phenol, 2-chloro-3-methoxy-5-
methylphenol, phthalic acid and N,N- 3.S.2
dimethyl-p-toluenesulfonamide (Gavin and Naphthaquinones and
Tabacchi 1975), and a,a-dimethylstyrene, bis-Naphthaquinones
3,5-dimethylstyrene, 0- tert -butylphenol, p-
methylacetophenone, 1,4-diethylbenzene, 2- 7,7' -Bis( 1,4,5,8-tetrahydroxy-3-ethylnaphtha-
phenyldecane, 3-phenyldecane, 4-phenylde- 2,6-quinone) or
cane, 5-phenyldecane, 2-phenylundecane, 7,7' -Bis(2,S,6,8-tetrahydroxy-3-ethylnaphtha-
3-phenylundecane, 4-phenylundecane, 5-phe- 1,4-quinone)
nylundecane, 2-phenyldodecane, 3-phenyldo- [7,7' -Bis( 1,4,5,8-tetrahydroxy-3-ethylnaphtha-
decane, 4-phenyldodecane, 5-phenyldodecane, 2,6-chinon) or
1-phenyldec-3-ene, 5-phenylundec-3-ene, 2- 7,7'-Bis(2,5,6,8-tetrahydroxy-3-ethylnaphtha-
phenyltridecane, 4-phenyltridecane, 5-phenyl- l,4-chinon) ]
tridecane, 5-phenyldodec-3-ene, 2-chloroorci- C24HJSOl2 (498.38)
3.8 Quinones 165
React: KOH dirty green, NH 40H red-violet,

FeCl3 wine red, Mg(OAc)2 red-violet, U0 2(OAc)2
red-violet, Na 2B4 0 7 pink
UV (MeOH): S 214 (3.85), 242 (4.02),270 (3.87),
380 (3.25), 500 nm (3.09)
IR (KBr): 675, 750, 800, 816, 845, 880, 925, 962,
1090, 1115, 1182, 1228, 1255, 1280, 1340, 1380,
OH
1408, 1475, 1595, 1650, 2850, 2940, 3450 cm-1
lH-NMR (60MHz,DMSO-d6 ): 2.40 (3H,s,Me-1),
OH 5.98 (1H,s,H-3), 6.27 (1H,s,H-7), 7.13 (1H,s,
H-10)
MS, m/z: 272 (100%), 244 (93), 216 (70), 203
HO 0
(60),200 (44), 199 (44), 188 (53), 183 (26), 176
Red crystals (Et20), mp 265C (dec.) (32), 175 (32), 163 (22), 160 (32), 148 (13), 138
UV (MeOH): 216 (3.95), 242 (3.80), 333 (3.62), S (13), 121 (18), 120 (19), 111 (15), 110 (13), 109
457 (3.42),494 (3.52), 525 (3.57),562 nm (3.41) (15),98 (22), 97 (20), 96 (11),95 (22), 88 (31)
IR (KBr): 1298, 1413, 1460, 1598, 2872-2968, Deriv: Di-O-acetylcanarione, yellow prisms
3400, 3527 cm- 1 (CHCI 3 -MeOH), mp 217-218C, by acetylation
lH-NMR (DMSO-d6 ): 1.23 (6H,t,2x-Me), 2.66 of canarione with Ac20-H2S04
(4H,q,2x-CH 2-), 11.33 (s,-OH) StL: Lethariella canariensis (Ach.) Krog
13C-NMR (DMSO-d6 ): 12.5 (q), 16.1 (t), 102.9 (s), TLC: RF 0.38 (silica gel H with 0.5% EDTA, for-
109.9 (s), 115.5 (s), 127.3 (bs), 153.3 (bs), 154.9 mic acid: ethyl formate: benzene = 3: 25: 25)
(s), 165.3 (s), 166.0 (s), 171.2 (s), 172.3 (bs) HPLC: R]4
MS, m/z: 499 (26%),498, (M+,100), 497 (31),483 Lit: Huneck et al. 1977b
(4),482 (10),481 (12),480 (18), 479 (8),470 (12),
455 (13),452 (22),451 (15),424 (6),409 (7),249
(9),207 (7),181 (17),97 (7) Chiodectonic acid (Chiodectonsaure)
Deriv: Octaacetyl compound, mp lIS-118C
(Et20), from the pigment with Ac20-H2S04 C1sH lO 0 9 (334.23)
StL: Flavocetraria cucullata (Bell.) Karnef. et Likely structure:
Thell
Lit: Krivoshchekova et al. 1982 o HO
Canarione (Canarion)
Cl4 H s0 6 (272.20)
Dark red rhombic plates (acetone, acetone-

H 20), mp 294-296C
UV (MeOH): 287 (4.33), 510 (4.01), 538nm
(4.00)
IR (KBr): 736, 800, 816, 828, 854, 944, 970, 1008,
Orange platelets (acetone) which decompose 1042, 1076, 1120, 1176, 1290, 1410, 1456, 1534,
above 250C 1590, 1624, 1658,3000, 3340cm-1
MS, m/z: 334 (M+,100%), 319 (5), 316 (3), 291 354.5 (CHCI3, c 1.14), from haemoventosin with
(12), 288 (27), 287 (14), 273 (19), 263 (25), 245 Ac 20-H 2S0 4 at 20C in 24h
(5),207 (31), 192 (3),64 (7), 43 (27) IR (KBr): 724, 752, 780, 792, 826, 882, 958, 1012,
Deriv: Tetraacetylchiodectonic acid, yellow 1066, 1114, 1190, 1220, 1304, 1368, 1428, 1606,
prismatic needles (CH 2CI2-MeOH), mp 184- 1634, 1716, 1750,2950, 3480 cm-l
185C; from chiodectonic acid with Ac 20-H2S0 4 MS, m/z 346 (M+,100%), 333 (73), 304 (84), 302
IH-NMR (60MHz,CDCI3): 2.36 (s,3H,-OAc), (59), 289 (69), 288 (56), 287 (64), 286 (57),273
2.44 (s,6H,-CO-Me,-OAc), 2.49, 2.57, (2xs, (49),271 (53), 260 (48),245 (67),243 (46),217
2x3H,2x-OAc), 3.95 (s,3H,OMe) (30)
StL: Cryptothecia rubrocincta (Ehrenb.) Thor., +158 +406 +17 +1076 O -1412
ORD (MeOH): [(1.]----------
Pyxine coccifera (Fee) Nyl. , 500 438 376 314 300 294 nm
TLC: RF 0.55 (silica gel H with 0.5% ethyl- ~E +4,50 +2.24 +2.28 -2.64 +7.66
CD (acetonitri!e):
enediaminetetraacetic acid, benzene: HC0 2Et: 209 231 235 269 299 nm
HC0 2H=5:5:1) StL: Ophioparma ventosa (L.) Norm.
HPLC: Rt 3.76, R[ 11 TLC: A: 38, B: 2, B': 2, C: 20
Lit: Huneck 1976 Lit: Bruun and Lamvik 1971; Maximov et al.
1990; Rycroft et al. 1995
Haemoventosin
4'-Hydroxy-8-methoxytrypethelone
methyl ether (4'-Hydroxy-8-
o OH 0 methoxytrypethelonmethylether)
ClsH2006 (332.34)
M~O Me
OH
Reddish brown rhombohedral crystals, shim-

mering like bronze (benzene). mp 202-204C
(dec.)
UV (EtOH): 235 (4.43),294 (3.97), 505nm (3.90)
IR (KBr): 704, 720, 748, 788, 816, 838, 870, 950, Red needles (toluene-n-pentane), mp 182-
1002, 1060, 1110, 1180, 1220, 1240, 1300, 1364, 183C, [am + 218 (MeOH, c 0.0045)
1424, 1450, 1564, 1608, ~634, 1722, 1758, 2950, UV (MeOH): 277 (4.34), 368 (3.31), 472nm
3550cm- 1 (3.46)
IH-NMR (100MHz,CF 3COOH): 1.68 (3H,d, IR (KBr): 890, 945, 985, 1020, 1070, 1105, 1265,
J=7Hz, Me-ll), 2.92 (1H,dd,J4A,3=11.5,J4A,4B= 1290, 1355, 1385, 1420, 1455, 1485, 1570, 1610,
18.5Hz,H-4A), 3.56 (1H,dd,J4B,3=3.5Hz,J4B,4A= 1650, 1690, 2965, 3560 cm- 1
18.5Hz,H-4B), 4.11 (3H,s,C-7-0Me), 6.63 IH-~MR (90MHz,acetone-d6): 1.31 (3H,s,Me-
(IH,s,H-8) 5'), 1.61 (3H,d,Me-1'), 2.59 (3H,d,Me at C-5),
MS, m/z 304 (M+,100%), 302 (52), 260 (88) 3.74 (2H,m,-CH 2-4'), 3.79 (3H,s,-OMe at C-8),
Deriv: 10-0-Acetylhaemoventosin, mp 203- 3.94 (3H,s,-OMe at C-7), 4.71 (IH,q,H-2'), 7.13
204C (yellow needles from MeOH), [aHis + (lH,bs,H-6)
3.8 Quinones 167
MS, m/z 334 (37%), 332 (M+,l1), 302 (29), 301 o HO

(100),287 (21),274 (11)
StL: Mycobiont of Trypethelium eluteriae
Sprengel
Lit: Mathey et al. 1980
Red needles (by sublimation i.vac.), mp > 360C
8-Methoxytrypethelone methyl ether (dec., darkens from 260C)
(8-Methoxytrypethelonmethylether) UV (MeOH): 294 (4.37), S 318 (4.18), S 328
(3.99), 449 nm (3.65)
ClsH200S (316.34)
IR (KBr): 692, 772, 816, 862, 892, 938, 978, 1020,
13 1054, 1092, 1110, 1180, 1220, 1290, 1310, 1442,
CH 30 0
12 1540, 1610, 1630,2950,3150, 3450cm-1
CH 30 ::? 8 9 1 2 0
MS, m/z 318(M+), 272, 257, 247
7 I lCH 3
6~ h Deriv: Tri-O-methylrhodocladonic acid, mp
5 14 3' CH 3
192-193C, by methylation of rhodocladonic
CH 3 0 2' 5'
11 CH acid with CH 2N2 in MeOH
l' 3 IH-NMR (60MHz, CDC13 ): 2.58 (s,3H,1-Me),
Red plates (toluene-n-pentane), mp 165-166C, 8.02 (s,lH,10-H). Triacetylrhodocladonic acid,
[am + 62 (MeOH, c 0.01) yellow prisms (EtOH), mp 210-212 DC, by acety-
UV (MeOH): 278 (4.56), 363 (3.47), 478nm lation of rhodocladonic acid with Ac 20-H 2S0 4
(3.61) StL: Cladonia deformis (L.) Hoffm., Cladonia
IR (KBr): 785, 880, 935, 990, 1010, 1040, 1070, jloerkeana (Fr.) Florke
1110, 1265, 1355, 1420, 1450, 1490, 1575, 1610, Lit: Baker and Bullock 1969; McLean et al. 1983
1645, 1700, 2890, 2960, 3005 cm-1
IH-NMR (90MHz,acetone-d6 ): 1.21 (3H,s,Me- 1,4,5,8-Tetrahydroxy-3-ethylnaphtho-2,6-
4'), 1.38 (3H,s,Me-5'), 1.46 (3H,d,Me-1'), 2.60 quinone or
(3H,d,Me-ll), 3.80 (3H,s,-OMe-8), 3.94 (3H,s,- 2,5,6,8-Tetrahydroxy-3-ethylnaphtho-1 ,4-
OMe-7), 4.69 (1H,q,H-2'), 7.15 (1H,bs,H-6) quinone (1,4,5,8-Tetrahydroxy-3-
13C-NMR (CD 30D): C-1: 184.0, C-2: 177.2, C-3: ethylnaphtho-2,6-chinon oder
123.0, C-4: 174.2, C-5: 138.0, C-6: 121.6, C-7: 2,5,6,8-tetrahydroxy-3-ethylnaph tho-1,4-
158.4, C-8: 153.0, C-9: 126.1, C-10: 118.9, C-l1: chinon)
22.8, C-12, C-13: 56.8, 61.5, C-1': 25.9, C-2':
94.1, C-3': 44.0, C-4': 14.9, C-5': 20.5 C12 H lO 0 6 (250.20)
MS. m/z: 318 (17%),316 (5), 303 (19), 301 (2), OH OH 0 OH
273 (10), 28 (100)
CD (MeOH): L1c480 1.34, L1c370 0.23, L1c330 - 0.46, J-. 6 0 C2H5WOH
L1c302 0.65, L1c2S0 - 0.72, L1c255 1.23
or I I
HO h
OH OH 0 OH
Sprengel
Lit: Mathey et al. 1980 Red crystals (EtOH), mp 183-185C
UV (MeOH): 217, S 241, 266, S 485, 517, 555nm
MS, m/z: 250 (M+,100%), 235 (37),232 (10), 217
Rhodocladonic acid (Rhodocladonsaure) (12),209 (2),207 (3),203 (5), 193 (5), 156 (7), 142
ClsHlOO S (318.23) (5), 137 (5), 124 (5)
Deriv: Di-O-methylether, mp 163-164 C, by Trypethelone methyl ether

methylation of the pigment with CH2 N2 (Trypethelonmethylether)
StL: Flavocetraria cucullata (Bell.) Karnef. et
C17H 1s0 4 (286.31)
Theil
Lit: Krivoshchekova et al. 1982 o
Trypethelone (Trypethelon)
Cl6Hl604 (272.29)
Red-violet needles (toluene-n-hexane), mp 140-

142C, [am + 110 (MeOH, c 0.0036)
UV (MeOH): 273 (3.63), 281 (3.64), 314 (3.05),
499 nm (2.45)
IR (KBr): 790, 890, 980, 1030, 1070, 1120, 1145,
Black-violet prisms (CHCI 3-n-hexane), mp 264- 1180, 1255, 1340, 1380, 1395, 1455, 1555, 1590,
266C, [a]f? + 364 (MeOH, c 0.0024) 1610,1640, 1650,2960, 3000cm-1
UV (MeOH): 274 (4.54), 283 (4.55), 316 (3.89), lH-NMR (90MHz,acetone-d6): 1.22 (3H,s,Me-
516nm (3.51) 4'), 1.39 (3H,s,Me-5'), 1.47 (3H,d,Me-l'), 2.61
IR (KBr): 685, 800, 875, 1035, 1120, 1145, 1185, (3H,d,Me-11), 3.92 (3H,s,-OMe-7), 4.72 (IH,
1215, 1230, 1295, 1315, 1380, 1455, 1535, 1620, q,H-2'), 7.08 (IH,dd,H-6), 7.39 (IH,d,H-8)
1695, 2950, 3000, 3200 cm- 1 MS, m/z: 288 (13%),286 (M+,100), 271 (95),258
lH-NMR (90MHz,acetone-d6): 1.22 (3H,s,Me- (41)
4'), 1.40 (3H,s,Me-5'), 1.47 (3H,d,Me-l'), 2.56 StL: Mycobiont of Trypethelium eluteriae
(3H,d,Me-11), 4.70 (IH,q,H-2'), 6.96 (IH,dd, Sprengel
H-6), 7.35 (IH,d,H-8), 9.14 (IH,s,-OH) Lit: Mathey et al. 1980
13C-NMR (acetone-d6): C-l: 183.7, C-2: 176.8,
C-3: 122.7, C-4: 175.0, C-6: 124.9, C-7: 162.4, 3.B.3
C-8: 116.6, C-9: 135.6, C-I0: 118.1, C-l1: 22.3, Anthraquinones, Anthrones,
C-l': 26.0, C-2': 94.3, C-3': 43.9, C-4': 14.9, C- bis-Anthraquinones and bis-Anthrones
5': 20.5
MS, m/z: 274 (5%), 272 (M+,38), 257 (35), 244 Asahinin
(21),229 (100)
CD (MeOH): LlC480 1.50, LlC340 0.29, Llc315 0.65,
LlC255 1.38
HO~Me
Sprengel
Lit: Mathey et al. 1980
OH 0 OH
Crystals, mp > 320C

UV (EtOH): 228, 261, 302 nm
3.8 Quinones 169
StL: Asahinea chrysantha (Tuck.) W.Cu:lb. et Bellidiflorin

C.Culb.
Bellidiflorin is quite likely an iron complex of
Lit: Stepanenko et al. 1985
acetylgraciliformin:
Averantin
HO
o
Orange needles, mp 233-234C, [aW9 - 178
(EtOH)
UV (EtOH): 223 (4.53), S 258 (4.18),266 (4.24), S
287 (4.47),294 (4.53), 325 (4.01), 4.54nm (4.03) Rhombic brown prisms (benzene or acetone),
IR (KBr): 1620, 1650cm-1 mp > 270C, [a]D - 380 (dioxane)
MS, m/z: 354 (M-H 20), 325, 311, 300, 289, 274 UV (dioxane): 253, 387, S 465nm
StL: Solorina crocea (1.) Ach. IR (CHCI3): 1226, 1615, 1702, 1745cm-1
TLC: RF 0.25 (Silica gel 60, Merck, benzene: ORD (dioxane): [a]253 + 7640, [alz67 + 4370, [a]272
HC0 2C2H s : HC0 2H = 80: 20: 1) + 5680, [aLsl 0, [a]2SS - 5680, [a]296 0, [aLo6 +
Lit: Steglich and Jedtke 1976 4590, [aLs + 3930, [aL33 + 5900, [a]3S7 0, [aL73
- 7210, [aLS4 0, [a]407 + 10900, [a]429 + 3930,
[a]444 0, [a]474 - 4100, [a]SI9 0, [a]S4S + 786,
Averythrin [a]sso 0, [a]628 - 1070
C2oHIS06 (354.34) StL: C.bellidiflora (Ach.) Schaer., Cladonia
graciliformis Zahlbr.
OH a OH MC: Fig. 58A
~CH=CH-(CH2)3-Me Lit: Zopf 1907; Ejiri et al. 1975; Alagna et al. 1990
HO~OH
o 7-Chloroemodin (7-Chloremodin)
Red prisms, mp 229-231 c (dec.) C Is H 9CIO s (304.67)

UV (EtOH): 223 (4.46), S 25~ (4.12),266 (4.17),
H:~M'
294 (4.45), 324 (4.02), 453 nm (3.95)
Deriv: Tetraacetylaverythrin, yellow needles,
mp 198-200C, from averythrin with Ac 20-
H 2 S0 4 a
StL: Solorina crocea (1.) Ach. Orange ,needles (MeOH), mp 286-287C
TLC: A: 42, B': 53, C: 25, E: 9 React: Mg(OAc)2 pink-red
Lit: Buckingham 1994a UV (EtOH): 220.5 (4.45),255 (4.16),273 (4.32),
282 (4.33), S 308 (4.07),437 (4.01), 458 (3.96), S
515nm (3.17)
IR (KBr): 1611, 1663,3333 cm-1 Orange needles, mp 287-288C

IH-NMR (300MHz,acetone-d6): 2.50 (3H,s,- UV (EtOH): 221 (4.41),252 (4.19), S 266 (4.16),
Me), 7.19 (lH,s,H-2), 7.45 (lH,s,H-5), 7.60 (lH, 290 (4.19),438 (3.95), S 458 (3.94)
s,H-4), 11.90 (lH,s,HO-1) IR (KBr): 1595, 1630, 1674,3432, 3508cm-1
!3C-NMR (l25MHz,DMF-d6): C-1: 163.1, C-2: MS, m/z: 286 (M<-), 257
108.7, C-3: 162.8, C-4: 121.4, C-5: 124.8, C-6: StL: Xanthoria parietina (1.) Th.Fr.
149.7, C-7: 121.3, C-8: 160.8, C-9: 191.0, C-lO: Lit: Piattelli and Giudici de Nicola 1968
181.7, C-11: 133.0, C-12: 114.2, C-13: 110.1, C-
14, 133.2, -Me: 22.0 Cynodontin
MS, m/z 304 (M+)
StL: Heterodermia obscurata (Nyl.) Trev., C1SHlQ06 (286.23)

Nephroma laevigatum Ach. OH 0 OH
TLC: A: 53, B': 56, C: 45, E: 11; RF 0.72 (CHCI3 :
MeOH = 4: 1) I I":
HPLC: R,38 :::,... h CH
3
Lit: Sargent et al. 1970; Cohen and Towers 1995a OH 0 OH
Bronze needles, mp 264C
Chrysophanol React: Mg(OAc)2 (EtOH) sky-blue
UV (EtOH): 241 (4.56),295 (4.06), S 471 (4.06),
C1sHlQ04 (254.23)
483 (4.14), S 503 (4.31), 514 (4.38), 539 (4.37),
\ \":
552nm (4.42)
Ci
OH 0 OH
IR (KBr): 1576cm-1
IH-NMR (90MHz,CDCU: 2.37 (3H,s,-Me),
:::,... ~ CH 12.39 (2H,s,2x-OH), 12.42 (2H,s,2x-OH)
3
MS, m/z 286 (M+,lOO%), 270, 257, 229
o StL: Asahinea chrysantha (Tuck.) W.Culb. et
C.Culb.
Yellow plates (EtOH), mp 193-196C
React: Mg(OAc)2 pink-red
UV (EtOH): 228 (4.30), 257 (4.01), 277 (4.03),
287 (4.03), 429nm Diacetylgraciliformin
IR (KBr): 1611, 1632, 1680 cm-1 C34H26012 (626.55)
StL: Acroscyphus sphaerophoroides Lev.
HO
Citreorosein
o
OH 0 OH
3.8 Quinones 171
Yellow crystals (acetone-EtOH), mp > 270C, 7,7'-Dichlorohypericin (7,7' -Dichlorhypericin)

[a]D + 392 (dioxane)
UV (dioxane): 253 (4.44), inflexion 278 (4.29),
386.5 nm (4.41)
IR (KBr): 1221, 1608, 1703, 1745cm-1 CI
ORD (dioxane): [<1>]252 + 6.12 x 10\ [<1>]257 + 4.54
x 10\ [<1>]268 + 7.94 x 10\ [<1>1zs0 0, [1z87 - 4.76 x HO
10\ [Loo 0, [<1>]315 + 2.27 x 104, [<1>]343 0, [<1>]378-
3.90 x 10\ [<1>]4030, [<1>]416 + 2.09 X 104 HO
MS, m/z: 626 (M+), 566, 506, 254 (lOO%)
StL: Cladonia graciliformis Zahlbr. CI
Lit: Ejiri et al. 1975
Black needles, mp > 350C (dec.)

5,7-Dichloroemodin (5,7-Dichloremodin) UV (DMSO): 251 (4.69), 294 (4.60), 332 (4.50),
CI5H8Cl205 (339.12) 388 (3.92),485 (4.07),553 (4.29), 597nm (4.57)
IH-NMR (400MHz,DMSO-d6): 2.65 (6H,s,2x-
Me), 7.42 (2H,s,H-2,H-2'), 13.79 (2H,s,HO-l,
CI~ HO-l'), 15.88 (2H,s,HO-8,HO-8'), 18.28 (2H,
s,HO-6,HO-6') MS (LSIMS), m/z 575 (M-H-,
HO~Me 20%),573 (39),571 (50)
CI 0 StL: Nephroma laevigatum Ach.
TLC: RF 0.3 (CHCI3 :MeOH = 4: 1)
Orange needles (benzene), mp 267-269, 274- HPLC: RT 13.55 min (Waters and Bondapak C1S -
275C column, gradient elution with MeOH: H 20 = 3: 2
UV (EtOH): 263 (4.34),320.5 (4.22),455 (3.98), S to MeOH in 10min)
525 nm (3.88) Lit: Cohen and Towers 1995a,b
IR (KBr): 1623, 1666,3317 cm- I
IH-NMR (400MHz,acetone-d6): 2.40 (3H,s,-
Me), 6.95 (IH,s,H-2), 7.43 (lH,s,H-4), 11.72 1,8-Dihydroxy-6-methoxy-3-(3' -oxobut-l'-
(lH,s,HO-l), 12.80 (lH,s,HO-8), 13.66 (lH,s, enyl)-anthraquinone
HO-6) 1,8-Dihydroxy-6-methoxy-3-(3' -oxobut-l'-
MS, m/z 342, 340, 338 (M+) enyl)-anthrachinon
Deriv: Triacetyl-5,7-dichloroemodin, yellow CI9HI406 (338.30)
needles (benzene-n-hexane), mp 218-219C,
from 5,7-dichloroemodin with Ac 20-HCI0 4
StL: Heterodermia obscurata (Nyl.) Trev.
TLC: RF 0.32 (CHCI3:MeOH = 4: 1) l' 3'
CH=CH-CO-CH3
HPLC: Rt 2.968 min (Waters and Bondapak C1S -
column, gradient elution with MeO: H 20 = 3: 2 o
to MeOH in 15min) Orange crystals, mp 261-262 C
Lit: Lam et al. 1972; Cohen and Towers 1995b MS, m/z: 323, 295
StL: Xanthoria parietina (1.) Th.Fr.
Lit: Piattelli and Giudici de Nicola 1968
2,7-Dimethoxy-3-methyl-5-hydroxy-6- HPLC: Rr 59
ehloroanthraquinone (2,7-Dimethoxy-3- Lit: Steglich and Jedtke 1976
methyl-5-hydroxy-6-ehloranthrachinon)
CI 7H13CIO s (332.72) Emodie acid (Emodinsaure)
o Cis H s0 7 (300.21)
MeO~OMe
C(~Me
OH 0
Physical data unknown

StL: Astroplaca opaca (Duf. ap Fr.) Bagl.
Orange needles, mp 363-365C
TLC: RF 0.81 (silica gel H, pretreated with
UV (EtOH): 222 (4.40),248.5 (4.18), 271.5 (4.18),
ethylenediaminetetraacetic acid, first to 10 cm
S 293 (4.14), 437nm (4.02)
with benzene: HC00 2H s = 1: 1, then to 15 cm
IR (KBr): 1625, 1670, 1700cm-1
with CHCI3)
MS, m/z: 300(M+), 283, 255
Lit: Yosioka et al. 1968b; Steiner et al. 1974
StL: Xanthoria calcicola Elenkin
Lit: Steiner and Hauschild 1970
4,4' -Disolorinic acid (4,4'-Disolorinsaure)
C42H3S014 (766.72) Emodin
OH 0 OH 0
ClsHIOOS (270.23)
OH 0 OH
Me
Orange-red needles (EtOH), mp 254-256, 259-

260C (dec.)
OH 0 OH 0 React: Mg(OAc)2 pink-red
UV (MeOH): 253 (4.31), 266 (4.29), 289 (4.36),
Red crystals, mp > 300(( 436nm (4.14)
UV (CHCI3): 243, 263, 270, 468nm IR (KBr): 1631, 1675, 3390cm-1
lH-NMR (CDCI3): 0.82 (6H,t,2x-Me), 1.2 [8H, lH-NMR (300MHz,acetone-d6 ): 2.47 (3H,s,-
m,2x-(CH 2-)2-]' 3.26 (4H,t,2X-CO-CH 2-), 3.80 Me), 6.65 (IH,d,J=2.5Hz,H-7), 7.15 (IH,s,H-2),
(6H,s,2x-OMe), 6.62 (2H,d,J=2Hz,H-7,H-7'), 7.25 (IH,d,J=2.5Hz,H-5), 7.58 (IH,s,H-4)
7.04 (2H,d,J=2Hz,H-5,H-5') 13C-NMR (125MHz,DMF-d 6 ): C-l: 167.0, C-2:
MS, m/z 766 (M+) 108.6, C-3: 165.9, C-4: 109.7, C-5: 121.5, C-6:
StL: Solorina crocea (1.) Ach. 149.3, C-7: 124.8, C-8: 161.9, C-9: 191.9, C-I0:
TLC: RF 0.95 (silica gel 60, Merck, benzene: 182.2, C-l1: 134.0, C-12: 114.4, C-13: 110.0, C-
HCOOCzHs:HCOOH = 80:20: 1) 14: 136.6, -Me: 21.8
3.8 Quinones 173
MS, m/z 270 (M+,1000/0), 242, 214 StL: Nephromopsis endocrocea (Asah.) Lai
Deriv: Tri-O-methylemodin, fine yellow TLC: A: 8, B: 33, B': 31, C: 6
needles, mp 224-226C (EtOAc-benzene), by Lit: c.P. Culberson 1969; Steglich and Reininger
methylation of emodin with dimethyl sulphate- 1970
K ZC0 3 in acetone
StL: Nephroma laevigatum Ach.
Erythroglaucin
TLC: A: 52, B: 61, B': 58, C: 38, E: 27
HPLC: RI 32 C16H I2 0 6 (300.26)
Lit: Sargent et al. 1970; Cohen and Towers 1995a
Emodinaldehyde (Emodinaldehyd)
C1s H s0 6 (284.21)
OH 0 OH
Mr\
Deep red plates (AcOH), mp 205-206C
UV (EtOH): 231 (4.44), 255 (4.17), 275 (4.13),
HO~CHO 302.5 (3.92), S 460 (3.95), S 475 (4.01),489 (4.08),
o S 511 (3.95), 523 nm (3.90)
IR (KBr): 615, 640, 758, 785, 815, 870, 905, 918,
Orange-yellow crystals, mp 272-274C 945, 993, 1020, 1038, 1090, 1130, 1155, 1180,
UV (MeOH): 221, 248, 267, 287, 434nm 1205, 1230, 1260, 1305, 1390, 1435, 1595 cm- 1
StL: Xanthoria calcicola Elenkin IH-NMR (CDCI 3): 2.33 (3H,s,-Me), 3.93 (3H,s,-
Lit: Hauschild et al. 1971 OMe), 6.67 (lH,d,J=2Hz,H-7), 7.06 (lH,s,H-2),
7.35 (lH,d,J=2Hz,H-5), 12.29, 12.37, 13.30
(3x1H,3xs,3x-OH)
Endocrocin
MS, m/z 300 (M+), 282, 270, 260
StL: Xanthoria elegans (Link) Th.Pr.
$ "':
Lit: Hauschild et al. 1971; Braun 1981
OH 0 OH
C02H
Pallacinal
I I
HO::::'" ~ CH
3 C 16 H lO 0 6 (298.24)
o
Orange-red crystals (acetone-H 20), mp 340C
(dec.)
React: K violet, Mg(OAc)z (EtOH) orange-red
UV (MeOH): 274 (4.32), S 287 (4.18), S 311
(3.92), 442nm (4.02)
IR (KBr): 1615, 1666, 1718, 3390cm-1 Orange7red needles (CHCI3 -EtOH), mp 250-
MS, m/z: 314 (M+,50/0), 296 (8),270 (100) 252C
Deriv: Triacetylendocrocin, faint yellow needles UV (EtOH): 244, 264, 280, 340, 425nm
(acetone-MeOH), mp 212C, by acetylation of IR (KBr): 1625, 1675, 1720cm-1
endocrocin with ACzO-pyridine MS, m/z: 298, (M+), 297, 269
StL: Xanthoria fallax (Hepp) Am., Xanthoria Greenish yellow needles (AcOH), mp > 360C
parietina (1.) Th.Fr. (darkening from 195C), [aJD + 30 (acetone, c
TLC: A: 62, B': 38, C: 57, E: 24, G: 65 0.1)
Lit: C.F. Culberson 1969; Hirose et al. 1982 UV (EtOH): S 233 (4.59), 281 (4.27), 370nm
(4.33)
IR (KBr): 1626,3400, 3470cm-1
Fallacinol, Teloschistin
IH-NMR (l00MHz,acetone-d6): 4.34, 4.60 (2x
C I6 H 12 0 6 (300.26) IH,2xd,J=3Hz,H-I0,H-1O'), 5.30 5.38 (2xlH,
2xbs,H-4,H-4'), 6.51 (2H,bs,H-2,H-2'), 7.19
(IH,s,H-5), 12.21, 12.42, 12.63, 12.85 (4xlH,
4xs,4x-OH)
MS (LSIMS), m/z 615 (M-H-,2%), 613 (4), 611
(5), 326 (19), 324 (75), 322 (100), 290 (9), 288
(18)
Orange needles (benzene), mp 244-246C
TLC: RF 0.42 (CHCI3 :MeOH = 4: 1)
React: K2C0 3 (2% solution in H 20) deep purple HPLC: Rt 3.76min (Waters-Bondapak column
red with MeOH-2% AcOH: acetonitrile = 1 : 1)
UV (EtOH): 224 (4.49), 250 (4.21), 265 (4.23), Lit: C.F. Culberson 1970a; Cohen and Towers
287 (4.21),433 (4.06), S 455nm (4.03)
1995b
IR (KBr): 1624, 1631, 1670,3450, 3520cm-1
Deriv: Triacetylfallacinol, pale yellow needles
(MeOH), mp 194-196C, by acetylation of Flavoobscurin Br
fallacinol with Ac2 0-pyridine
C30HlsCl40s (648.27)
StL: Teloschistes flavicans (Sw.) Norm.,
Xanthoria fallax (Hepp) Am. OH
TLC: A: 44, B': 31, C: 36, E: 13
HPLC: Rr 24
Lit: C.F. Culberson 1969; Sargent et al. 1970; OH
Hirose et al. 1982
OH
Flavoobscurin A Cl
C30H19Cl30s (613.82) OH
Yellow crystals, mp > 360C (darkening from
OH OH
210C), [aJD + 35 (acetone, c 0.1), sensitive to
light
OH UV (EtOH): S 233 (4.60), 286 (4.26), 377nm
(4.35)
IR (KBr): 1628, 3425 cm- 1
Me OH IH-NMR (400 MHz, acetone-d6): 2.32 (6H,s,
2x-Me), 4.95 (2H,s,H-I0,H-1O'), 5.74 (2H,s,
H-4,H-4'), 6.68 (2H,s,H-2,H-2')
OH 0 OH MS, m/z 328, 326, 324
3.8 Quinones 175
S.1L: Heterodermia obscurata (Nyl.) Trev. Yellow crystals (Et10 or CHC13), mp 267-268 DC
TLC: RF 0.2 (CHC13:MeOH = 4: 1) UV (CHC13: 271.5 (4.56),312.5 (4.14), 434.5nm
Lit: C.F. Culberson 1970a; Cohen and Towers (4.17)
1995b IR (KBr): 1630, 1680 cm-1
IH-NMR (100MHz,CDC13, 80 DC): 2.42 (3H,s,-
Me), 4.08 (3H,s,-OMe), 7.10, 7.63 (2xlH,2xd,
Flavoobscurin B2
J=IHz,H-2,H-4), 7.47 (1H,s,H-5), 11.86, 12.70
C30HlsC140s (648.27) (2xIH,2xs,2x-OH)
MS, mlz 318 (M+,65%), 284 (100),277 (3),275
OH 0 OH (10)
Cl Deriv: Diacetylfragilin, yellow needles (ac-
etone), mp 234-235 DC, by acetylation of fragilin
OH with AczO- Py
StL: Sphaerophorus fragilis (1.) Pers., S.globosus
(Huds.) Vain.
OH TLC: A: 75, B: 82, B': 67, C: 82, E: 54
HPLC: Rt 16.77, R] 50
Cl Lit: C.F. Culberson 1969; Sargent et al. 1970
OH 0 OH
Flavoobscurin Bl is a stereoisomer of fla- Graciliformin

voobscurin Bl
Yellow crystals, mp > 360 DC (darkening from
215 DC), [al D + 7 (acetone, c 0.10)
UV (EtOH): inflexion 232 (4.61), 276 (4.27),
383 nm (4.32)
IR (KBr): 1631,3385, 3465cm-1
IH-NMR (100MHz,DMSO-d6 ): 1.96 (6H,s, o
2xMe), 4.93 (2H,s,H-1O,H-1O'), 5.42 (2H,bs,H-
5,H-5'), 6.60 (2H,bs,H-7,H-7'), 11.05, 12.46 o
H.
(2x1H,2xs,2x-OH)
MS, m/z 328, 326, 324
Lit: C.F. Culberson 1970a OH 0 OH
Yellow crystals (acetone EtOH), mp > 270 DC

Fragilin UV (dioxane): 251 (4.23), inflexion 275 (4.07),
Cl 6HllClO s (318.70) 387.5nm (4.19)
IR (KBr): 1618, 1703cm-1
OH 0 OH
MS, m/z 542 (M+), 270,254 (100%)
StL: Cladonia graciliformis Zahlbr.
Lit: Ejiri et al. 1975
Haematommone (Haematommon) 5), 7.24 (lH,m,h,s=1.4Hz,J7,?1.4Hz,H-7), 10.25,

11.48, 11.52 (3x1H,3xs,3x-OH)
Cl6 H lO 0 7 (314.04)
MS, m/z 270 (M+,1000/0), 253, 242, 213
Deriv:Triacetylislandicin, mp 206-207C, from
islandicin with ACzO-H zS0 4
StL: Asahinea chrysantha (Tuck.) W.Culb. et
C.Culb.
HO
Lit: Mishchenko et al. 1980; Wiseman et aI. 1980
Red needles (acetone), mp > 300C (dec.) 6-0-Methylaverantin

UV (MeOH): 205 (4.67), 235 (4.71), 269 (4.43),
281 (4.43), 310 (4.63), 464nm (4.18); MeOH + Cz1 H 22 0 7 (386.38)
AICI 3: 208 (5.19), 233 (4.63), S 272 (4.44), 327
(4.78), 544nm (4.20)
IH-NMR (400MHz,DMSO-d6): 2.55 (3H,s,-Me),
6.51, 7.14 (2x1H,2xd,H-5,H-7), 7.17 (lH,s,
-H-4) o
StL: Haematomma puniceum (Sm. ex Ach.)
Massal. Yellow crystals, mp 213 DC, [ams - 176.5 (EtOH)
TLC: RF 0.36 (silica gel, n-hexane: EtzO: HCOOH UV (MeOH): 223, S 250, 292.5, 318, 445nm
= 15:10:3) IH-NMR (100MHz,acetone-d6): 0.86 (3H,t,J=
Lit: Huneck et al. 1991a 7Hz,Me-), 1.4 [4H,m,-(CH 2 )z-]' 1.84 (2H,m,-
CH2-), 2.50 (2H,m,-CH z-), 3.98 (3H,s,-OMe),
5.46 (lH,dd,-CHOH-), 7.14 (lH,s,H-4), 6.73
Islandicin (lH,d,J=2Hz,H-7), 7.26 (lH,d,J=2Hz,H-5)
MS, m/z 368 (M-H 20), 339, 325, 311, 286
StL: Solorina crocea (1.) Ach.
OH 0 OH TLC: RF 0.74 (silica gel Merck, benzene:
7*1
1
6:::,...
5
":2
h CH
3
HCOOC 2Hs :HCOOH = 80:20:1)
Lit: Steglich and Jedtke 1976
o OH 6-0-Methylaverythrin
Dark red plates, mp 218C C21H2006 (368.37)
React: Mg(OAc)2 (in EtOH) raspberry red
UV (EtOH): 231 (4.56),251 (4.34),289 (3.93), S
460 (4.01), S 479 (4.08), 491 (4.14), 513 (4.00),
527 nm (3.99)
IR (KBr): 675, 732, 790, 810, 890, 915, 977, 1015,
1080, 1175, 1250, l318, l385, 1445, 1600, o
3400cm-1 Orange-red crystals (MeOH), mp 215C
IH-NMR (90MHz,CDCI3 ): 2.21 (3H,s,Me-3), React: Mg(OAc)2 (EtOH) purple
7.10 (lH,s,H-2), 7.65 (lH,t,J6,S=8.2Hz,J 6,7= UV (dioxane): 223, S 255, 267, 292, 320, 445nm
7.6Hz,H-6), 7.85 (lH,m,Js,7=1.5Hz,Js,6=7.5Hz,H- IR (KBr): 1610, 1670 cm- l
3.8 Quinones 177
H:#M.
IH-NMR (l00MHz,acetone-d6): 0.90 (3H,t,J=
7Hz,Me-), 1.38 [4H,m,-( CH2- )2-]
1.83 (2H,m,-CH 2 -CH=), 3.98 (3H,s,-OMe), 5.42,
6.10 (2H,m,-CH=CH-), 7.13 (IH,s,H-4), 7.24,
6.75 (2H, d,H-5, H-7), 10.68, 12.23, 12.69 o
(3xlH,3xs,3x-OH)
MS, m/z: 368 (M+, 68%), 353 (4), 339 (28), 325 Yellow crystals, mp 279-281 DC
(48),311 (100),300 (56),286 (16) UV (EtOH): 256 (4.24),286 (4.23), 423nm (3.77)
Deriv: Averythrin, red prisms, mp 229-231 DC IR (KBr): 1620, 1660cm-I
(dec.), by demethylation of averythrin-6- IH-NMR (300MHz,acetone-d6): 2.50 (3H,s,-
monomethylether with HBr in AcOH Me), 4.00 (3H,s,-OMe), 7.33 (IH,s,H-5), 7.42
StL: Solorina cracea (1.) Ach. (IH,s,H-2), 7.65 (1H,s,H-4)
TLC: A: 62, B': 61, C: 49, E: 31 I3C-NMR (125MHz,DMF-d6 ): C-l: 161.1, C-2:
HPLC: Rr 57 106.9, C-3: 162.1, C-4: 120.5, C-5: 120.8, C-6:
Lit: Ebizuka et al. 1970 148.3, C-7: 118.5, C-8: 160.9, C-9: 187.5, C-I0:
182.6, C-ll: 132.3, C-12: 114.2, C-13: 111.4, C-
14: 135.6, -Me: 21.9, -OMe: 56.9
1-0-Methyl-7 -chlorocitreorosein (1-0-Methyl- MS, m/z 318 (M+,100%), 300 (62), 290 (9), 289
7-chlorcitreorosein) (26), 283 (3),272 (72),260 (8), 247 (8)
C I6 H II CI0 6 (334.70) StL: Nephroma laevigatum Ach.
TLC: RF 0.7 (CHCI3 :MeOH = 9: 1)
HPLC: Rr 35
Lit: Bohman 1968; Cohen and Towers 1995a
1-0-Methylfragilin
C17HI3CIO s (332.72)
UV (EtOH): 222 (4.20), 300 (4.23), 434 (3.95),
452 (3.90),490 (3.77), 525 nm (3.60) CI$O
0 H O~H3
IH-NMR (300MHz,DMF-d6): 4.00 (3H,s,-OMe),
4.73 (2H,d,J=5Hz,-CH 2 -OH), 6.90 (lH,s,H-2),
I I
CH 0 ~ h CH
3 3
7.50 (1H,s,H-5), 7.80 (IH,s,H-4)
o
MS (CIMS), m/z 337 (M+H+,3%), 335 (12)
StL: Nephroma laevigatum Ach. Orange needles, mp 254-255 DC
TLC: RF 0.3 (CHCI 3 :MeOH = 9: 1) UV (EtOH): 289, 427 nm
HPLC: Rt 3.8 min (Waters and Bondapak C1S - IR: 1630, 1670 cm- I
column with MeOH-2% AcOH: acetonitrile = MS, m/z 334 (M+), 332, 316,314
1: 1) StL: Nephroma laevigatum Ach.
Lit: Cohen and Towers 1995a Lit: C.F. Culberson 1969
1-0-Methyl-7 -chloroemodin (1-0-Methyl-7- 8-0-Methylfragilin

chloremodin)
C17HI3CIO s (332.72)
CI 6HIICI0 s (318.70)
Yellow crystals (acetone-EtOH), mp > 270 DC

Cl$CH~
0 HO,,-,:
UV (dioxane): 251.5 (4.38), inflexion 278 (4.26),
I I 386.5nm (4.35)
CH 0 :::,... ~ CH
3 3 IR (KBr): 1226, 1611, 1704, 1748cm-1
o MS, m/z: 584 (M+), 524, 254 (100%)
StL: Cladonia graciliformis Zahlbr.
Yellow crystals, mp 234-236C Lit: Ejiri et al. 1975
UV (EtOH): 274, 417nm
MS, m/z: 332 (M+,100%), 314 (65), 304 (7), 303
(17),299 (8),297 (10),286 (41),273 (10),271 (8), Nemetzone (Nemetzon)
261 (9), 259 (12) Cl9Hl407 (354.30)
StL: Caloplaca xanthaspis (Krempelh.) Zahlbr.,
Nephroma laevigatum Ach. OH
Lit: Bohman 1968; Santesson 1970a
Monoacetylfallacinol
ClsHl407 (342.29)
Orange-red needles (CHC13-MeOH), mp 289-
290 DC
UV (MeOH): 215 (4.06), 245 (4.15), 283 (4.17),
355nm (3.42); MeOH + KOH: 208 (5.09), S 230
(4.69), S 257 (4.56), 305 (4.61), S 360 (4.24),
500nm (4.05); MeOH + AlC13: 217 (4.42), 250
(4.26),285 (4.28), S 360 (3.78), 475nm (3.64)
Orange crystals, mp 195-196 DC MS, m/z 354 (M+,3%) 352 (100), 323 (7), 309
StL: Xanthoria parietina (L.) Th.Fr. (14),281 (5),241 (5), 162 (11), 149 (6), 85 (16),83
Lit: Piattelli and Giudici de Nicola 1968 (15),69 (12), 57 (23), 43 (25)
Deriv: Acetylnemetzone, yellow needles
Monoacetylgraciliformin (CHC13-MeOH), mp 200-202 DC, by acetylation
of nemetzone with Ac20-H 2S0 4
C32 H24 0 11 (584.51) IH-NMR (500MHz, CDC13): 2.46 (3H,s,Me-'I"),
2.49 (3H,s,Me-CO-O- at C-8), 2.50 (3H,s, Me-
CO-O- at C-3), 3.98 (3H,s,-OMe), 6.18 (1H,
s,H-l), 6.95 (1H,d,J=2.4Hz,H-7), 7.67 (1H,d,
J=2.4Hz,H-5), 7.83 (1H,s,H-4)
CH 3 StL: Haematomma nemetzii Steiner
0 TLC: Rp 0.43 (silica gel, n-hexane: Et2 0: HCOOH
= 30:20:6)
0
H ..
CH 3
Norsolorinic acid (Norsolorinsaure)

OH 0 OH C2oHlS07 (370.34)
3.8 Quinones 179
OH 0 OH
~CO-n-C5Hll CI$O
0 0H
:
I I
HO~OH HO ~ h CH 3
o OH 0
Red needles (AcOH), mp 285-286 DC (with subli-
Red plates (EtOH), mp 269-270 DC mation from 235 DC)
UV (EtOH): 270 (4.32),286 (4.35), 312 (4.44), S React: NaHC0 3 purple, conc. H2S0 4 blue,
453 (3.95), 466nm (4.00) Mg(OAc)2 (EtOH) pink-violet
IR (KBr): 1625, 1680, 3400cm-' UV (MeOH): 239, 264, 307, 351, 465, 491, 520,
MS, m/z 370 (M+,300/0), 352 (10), 327 (38), 314 572nm
(20), 299 (100) IR (KBr): 710, 750, 785,870,935,960,1005, 1030,
StL: Lecidea piperis (Spreng.) Nyl., Solorina 1115, 1140, 1165, 1185, 1210, 1245, 1270, 1290,
crocea (1.) Ach. 1345, 1370, 1385, 1410, 1435, 1465, 1590, 1610,
TLC: A: 55, B': 66, C: 41, E: 19; RF 0.62 (silica gel, 2850, 2920, 3280 cm-1
benzene: HCOOC 2H 5: HCOOH = 80:20: 1) MS, m/z 320 (M+)
HPLC: R,46 Deriv: Tetraacetylpapulosin, yellow needles
Lit: Santesson 1969a; Steglich and Jedtke 1976 (MeOH), mp 221.5-222 DC, by acetylation of
papulosin with Ac2 0-HCI0 4 Tri-O-methylpa-
Oxyskyrin pulosin, yellow needles (EtOH-n-hexane), mp
180-180.5 DC, by treatment of papulosin with
C30H,sOll (554.44) dimethyl sulphate-K2C0 3 in refluxing acetone
for 2 days
StL: Lasallia papulosa (Ach.) Llano
Lit: Fox et al. 1969; Briggs et al. 1972; Lam et al.
1972
Parietin, Physcion
C16H 12 0 5 (284.26)
OH 0 OH
Orange-red needles, mp > 360 DC

React: Mg(OAc)2 (EtOH) orange, cone. H 2S0 4 o
red ---7 green Orange needles (acetone), mp 206-207, 209-
UV (EtOH): 257 (4.69), 300 (4.50), 462nm (4.37) 210 DC
StL: Trypetheliopsis boninensis Asah. React: KOH violet
Lit: Santesson 1970b uv (EtOH): S 257 (4.35), 266 (4.36), 288 (4.35),
431 (4.20)
IR (KBr): 665, 712, 756, 852, 878, 904, 930, 980,
Papulosin, Valsarin
1030, 1100, 1158, 1220, 1270, 1290, 1322, 1365,
C'5H9CI06 (320.67) 1385, 1480, 1562, 1625, 1670, 2960" 3550 cm-1
IH-NMR (400MHz,CDC13): 2.46 (3H,s,-Me), 1,4,5,6,8-Pentahydroxy-3-

3.94 (3H,s,-OMe), 6.69 (IH,d,J=2.4Hz,H-2), methylanthraquinone (1,4,5,6,8-Penta-
7.09 (lH,d,J=1.4Hz,H-7), 7.38 (IH,d,J=2.4Hz, hydroxy-3-methylanthrachinon)
H-4), 7.64 (IH,d,J=1.4Hz,H-5), 12.13, 12.32
Cls H lO 0 7 (302.23)
(2xIH,2xs,2x-OH)
MS, m/z 284 (M+,100%), 269 (11),256 (42),255 OH 0 OH
~
(89), 254 (36), 240 (5), 228 (12), 212 (65), 198
(34), 184 (56), 170 (9), 156 (22), 142 (27), 139
(73),128 (76), 127 (40), 91 (18),77 (65), 76 (29), HO~CH3
51 (76),50 (42) OH 0 OH
Deriv: Diacetylparietin, yellow needles, mp 185-
186C, by acetylation of parietin with Ac 20- Dark red crystals, mp > 315C
React: Mg(OAc)2 (EtOH) violet
pyridine
UV (EtOH): 247,261,302,500,540,565, 578nm
IR (KBr): 1584,3492 cm- 1
TLC: A: 75, B: 72, B': 71, C: 82, E: 59, G: 90; RF 0.85
MS, m/z: 302 (M+,100%), 286, 274, 245, 228
(silica gel, benzene: HCOOC 2H s : HCOOH = 74:
Deriv: Penta-O-methylether, mp 320C, from
25: 1),0.50 (silica gel, benzene: AcOH = 40: 3)
1,4,5,6,8 - pentahydroxy - 3 - methylanthra-
HPLC: R] 50
Lit: C.F. Culberson 1969; Sargent et aL 1970; quinone with CH2N2
StL: Asahinea chrysantha (Tuck.) W.Culb. et
Joshi et al. 1974
C.Culb.
Lit: Mishchenko et aL 1980
Parietinic acid (Parietinsaure)
Cl6 H lO 0 7 (314.24) Rugulosin
OH 0 OH C30H22010 (542.48)
~
CH30~C02H
o
Orange needles (AcOH), mp 304-305 c
UV (acetone): 325 (4.25), 435nm (4.30)
IR (KBr): 1629, 1700cm-1 o
Deriv: Methyl di-O-methylparietinate, yellow
needles (CHC13-EtOAc), mp 262-263C, by
methylation of parietinic acid with dimethyl
sulphate-K2C0 3 in acetone o
TLC: A: 40, B': 45, C: 47 Yellow crystals (EtOH), mp 293C (dec.), [alii +
HPLC: R] 22 492 (dioxane, c 0.5)
Lit: C.F. Culberson 1969; Sargent et aL 1970 IR (Nujol): 1620, 1690, 3360cm-1
IH-NMR (l00MHz,DMSO-d6 ): 2.42 (6H,s,Me-
7,Me-7'), 2.78 (2H,d,J=5.5Hz,H-3,H-3'), 3.38
(2H,bs,H-l,H-l'), 4.38 (2H,pd,J=5.5Hz,2-H,2'-
3.8 Quinones 181
H), 5.38 (2H,bs,OH-2,OH-2'), 7.16, 7.43 (4H, StL: Pyrrhospora russula (Ach.) Hafellner
2xd,J=IHz,H-6,H-6',H-8,H-8'), 11.37 (2H,s,- TLC: RF 0.55 (silica gel Merck 60F 254, toluene:
OH-5,OH-5'), 14.54 (2H,s,OH-4,OH-4') ethyl formiate: formic acid = 11 : 6: 3, rose-violet
Deriv: Tetrahydrorugulosin, pale yellow spot with NH3 vapours)
needles, mp 285C (dec.), [a]?J.5 + 210 (dioxane), Lit: Mathey 1986
by hydrogenation of (+ )-rugulosin with Pt - H2 in
EtOH
MS, m/z 542 (M+), 270, 256 Skyrin
C30HISOIO (538.44)
10i lJ-
[~]Xl0-4
I ~++-+-A--+---"-
-2
-4
250 300 350 400 450

A(nm)
OH 0 OH
ORD-curve of (+)-rugulosin
StL: Acroscyphus sphaerophoroides Lev. Yellow plates (Et20), mp > 360C
Lit: Kobayashi et al. 1970; Takeda et al. 1973; React: Mg(OAc)2 (EtOH) red, conc. H 2S04 red--?
Ph am van Chuong et al. 1973 emerald green, Na2C0 3 (H 20) deep purple
UV (EtOH): 218 (4.85), 259 (4.76), 298 (4.51),
462nm (4.38)
Russulone (Russulon)
IR (KBr): 740,1210,1250,1390,1470,1625,1680,
CI9 H 12 0 7 (352.29) 3440cm-1
CD (dioxane): [8]481 + 2080
MS, m/z 410,398,370,342
StL: Acroscyphus sphaerophoroides Lev.
/I 3/1 TLC: A: 37, B: 32, B': 35, C: 23, E: 4, G: 66
ME' HPLC: RI 31
o Lit: C.F. Culberson 1969; Hatfield and Slagle
1973
Red substance
UV (CHC13): 282, 384, 443nm
IH-NMR (400MHz,CDC13): 2.59 (3H,s,Me-3"), Skyrinol
3.92 (3H,s,MeO-), 6.32 (1H,s,H-l"), 7.66 C30Hls012 (570.44)
(1H,s,H-4), 6.73, 7.33 (2xlH,2xd,J=2.5Hz,H-
5,H-7), 13.20, 13.90 (2xIH,2xs,2xHO-)
MS, mlz 352 (M+,lOO%), 338 (8), 323 (8), 309
(12),249 (10), 248 (52),207 (10),204 (10),203
(42)
2,2',7,7'-Tetrachlorohypericin
(2,2',7,7'-Tetrachlorhypericin)
C30H12C140s (642.23)
o OH
HO
HO
Red crystals, mp > 360C CI CI

React: Mg(OAc)z (EtOH) orange, conc. H 2S0 4
red ---7 green OH 0 OH
UV (dioxane): 258, 290, 448nm Purple crystals (AcOH), mp > 350C (dec.)
IR (Nujol): 1608, 1631, 1691, 3436cm-1 UV (DMSO): 251 (4.69), 295 (4.60), 332 (4.50),
StL: Trypetheliopsis boninensis Asah. 390 (3.90), 484 (4.06), 554 (4.26), 598nm (4.55)
Lit: Santesson 1970b IH-NMR (400MHz,DMSO-d6 ): 2.80 (6H,s,2x-
Me), 13.95 (2H,s,HO-l,HO-l'), 15.65 (2H,s,
Solorinic acid (Solorinsaure) HO-8,HO-8')
MS (LSIMS), m/z 645 (M-H-,2%), 643 (6), 641
CZIHzo07 (384.37) (IO), 639 (7)
StL: Nephroma laevigatum Ach.
TLC: RF 0.2, (CHCI3:MeOH = 9: 1)
HPLC: ~ 14.177 min (Waters and Bondapak C1S-
column, gradient elution with MeOH : HzD = 3 : 2
to MeOH in 10 min)
Lit: Cohen and Towers 1995a,b
Orange red crystals (AcOH), mp 201C
UV (EtOH): 269 (4.43), 281 (4.40), 311 (4.45),
460nm (3.98) 1,5,6,8-Tetrahydroxy-3-methylanthraquinone
IR (KBr): 1624, 1681 cm-1 (1,5,6,8-Tetrahydroxy-3-methylanthrachinop.)
MS, m/z 384 (M+), 366, 341, 313 C ls H iO 0 6 (286.23)
Deriv: Triacetylsolorinic acid, yellow crystals
(benzene-n-hexane), mp 147C, by acetylation OH
of solorinic acid with ACzO-pyridine
StL: Solorina crocea (1.) Ach.
TLC: A: 80, B': 78, C: 85, E: 61. RF 0.94 (silica gel,
benzene:HCOOCzHs:HCOOH = 80:20: 1)
HPLC: Rr 75 Dark red crystals, mp > 320
Lit: Anderson et al. 1966 React: Mg(OAc)2 (EtOH) rasberry red
UV (EtOH): 258, 283, 310, 447, 500, 533nm
MS, m/z: 286 (100%), 270, 258, 257, 241, 229,
216,213,212,211,201,161,155,137,115,105,97
3.8 Quinones 183
StL: Asahinea chrysantha (Tuck.) W.Crilb et

C.Culb.
2,5,7 -Trihydroxyemodin
ClsHlOOS (318.23) Red crystals (toluene), mp 253 DC
UV (EtOH:dioxane = 10:1): 234 (4.50), 256
(4.55), 302 (3.79), 457 (4.06), 487 (4.15), 507
HO
(4.01), 520nm (4.01)
HO IR (KBr): 1597 cm- 1
IH-NMR (60MHz,CDC13): 2.46 (3H,s,-Me), 4.03
(3H,s,-OMe), 6.17 (IH,s,H-7), 7.15 (1H,s,H-2),
Red crystals (acetone), mp > 365 DC 7.73 (lH,s,H-4), 12.34, 12.88, 13.67 (3xlH,3xs,
UV (EtOH): 294, inflexion 313, inflexion 350, 3x-OH)
497nm Deriv: Triacetylxanthorin, yellow needles
IR (KBr): 1614, 1631 cm-1 (EtOH), mp 245-247 DC, by acetylation of
IH-NMR (DMSO-d6 ): 2.17 (3H,s-Me), 7.42 xanthorin with Ac 2 0-pyridine-HCI0 4 at room
(IH,s,H-4) temperature in 4 days
StL: Mycoblastus sanguinarius (1.) Norm. StL: Laurera purpurea (Nyl.) Zahlbr., Xanthoria
Lit: Bohman 1970 elegans (Link) Th.Fr.
TLC: RF 0.54 (silica gel, benzene: HCOOC 2Hs :
1,6,8-Trihydroxy-3-methyl-7-chloro-9- HCOOH = 75: 25: 1), 0.35 (silica gel, benzene:
anthrone (1,6,8-Trihydroxy-3-methyl-7-chlor- AcOH = 40:3)
9-anthron) Lit: Steglich et al. 1967; Stensi6 and
Wachtmeister 1969
Cls H u CI0 4 (290.69)
12
Cl@97
OH 0 OH
3
3.8.4
Biphenylquinones
3,6,3',6'-Tetrahydroxy-4-methyl-biphenyl-
HO 6 5 0 4 Me
H H 2,5,2',5'-diquinone (3,6,3',6'-Tetrahydroxy-4-
methyl-biphenyl-2,5,2',5' -dichinon)
StL: Astroplaca opaca (Duf. ap Fr.) Bagl., C13HsOS (292.20)
Heterodermia obscurata (Nyl.) Trev.
TLC: RF 0.52 (silica gel H, pretreated with
ethylenediaminetetraacetic acid, first to 10 cm
with benzene: HCOOC2 Hs = 1: 1, then to 15 cm
with CHCI3 )
Lit: Bohman 1968; Steiner et al. 1974
This structure had been erroneously assigned to

Xanthorin
pyxiferin
UV: 215 (4.55),321 (4.55), 530nrn (3.00)
IH-NMR (DMSO-d6 ): 1.83 (3H,s,-Me), 5.90 UV (EtOH): 217 (4.33), 264 (4.27), 305 (4.30),
(lH,s,H-4') inflexion 390 (3.48), 483 nm (3.86)
Lit: Kalamar et al. 1974 IR (KBr): 1610, 1645 cm-1
Deriv: Tetraacetylthelephoric acid, orange yel-
3.8.5 low needles (nitrobenzene), mp 330C, by acety-
Terphenylquinones lation of thelephoric acid with ACzO-pyridine
MS, mlz 187, 165, ISS, 128
Polyporic acid (Polyporsaure) StL: Lobaria retigera (Bory) Trev.
C1sH 12 0 4 (292.28)
3.8.6
Phenanthrenequinones
Biruloquinone (Birulochinon)
Cl7 H lO 0 7 (326.25)
Red needles (pyridine) or purple cubes (ac-
etone), mp 315C
UV (EtOH): 256 (4.63), 262 (4.63), S 330 (4.06),
Mew
0 OMe
o
OH
465nm (2.60)
IR (KBr): 1597,1613, 1637, 331Ocm-1 o
MS, mlz 292 (M+,50%), 290 (82), 149 (40), 145 OH 0
(100),117 (40), 89 (70) Dark violet crystals (dioxane), mp 307-308C
Deriv: Diacetylpolyporic acid, yellow needles UV (CHCI 3 ): 290 (4.03), 307 (4.17), 320 (4.12),
(benzene), mp 212C, by acetylation of poly- 440 (3.33), 568nm (3.42). MeOH: 234, 268, 323,
poric acid with ACzO-pyridine 403, 565nm
StL: Pseudocyphellaria coronata (Miill.Arg.) IR (CHCI 3 ): 784, 1195, 1366, 1473, 1555, 1600,
Malme 1628,1728,2840,2927,2960,3080cm-1
TLC: A: 29, B: 28, B': 29, C: 19 IH-NMR: 2.87 (3H,s-Me), 4.03 (3H,s,-OMe),
HPLC: Rt 3.18min 6.96, 7.02 (2xlH,2xs,2xarom.-H), 12.50, 12.66
Lit: C.P. Culberson 1969; Dallacker and Ditgens (2x 1H,2xs,2x-0 H)
1975 MS, m/z 326 (M+,100%), 298 (11), 297 (23), '280
(20),269 (14),252 (9), 241 (15)
Deriv: Diacetylbiruloquinone, yellowish crys-
Thelephoric acid (Thelephorsaure)
tals, mp 132-134C, from biruloquinone with
C1sHsOs (352.24) AC zO-H zS0 4
StL: Parmelia birulae Blenk.
TLC: RF A: 0.80, B: 0.13, C: 0.30
HO OH Lit: Krivoshchekova et al. 1983b; Arnone et al.
1991
HO OH
o
Brilliant dark violet crystals (pyridine), mp >
350C
3.9 Chromanes and Chromones 185
3.8.7 TLC: RF A: 0.78, B: 0.90, C: 0.77

Perylenequinones Lit: Hamat et al. 1993
Isohypocrellin
Eugenitin
C30H26010 (546.51)
C12H 120 4 (220.22)
Prismatic plates (acetone), mp 163C

UV (MeOH): 230 (4.41), 252 (4.36), 260 (4.34),
290 (4.13), S 330nm (3.60)
OH 0 IR (KBr): 670, 685, 710, 730, 782, 830, 850, 960,
1015, 1040, 1090, 1130, 1160, 1172, 1190, 1208,
Red substance 1270, 1300, 1340, 1372, 1400, 1442, 1470, 1502,
React: KOH green 1580, 1620, 1654, 2600, 2700, 2860, 2950, 3050,
UV (MeOH): 265, 285, 465, 538, 580 nm 3120, 3500cm-1
IH-NMR (400MHz,CDCI3): signals at 1.78, 1.82, IH-NMR (60MHz,CDCI3): 2.07 (3H,s,Me-1),
2.33,3.66,3.71,3.78,4.06,4.065,4.16,4.26,6.53, 2.33 (3H,s,Me-9), 3.88 (3H,s,MeO-7), 6.00 (lH,
6.55, 15.94, and 16.05 ppm s,H-3), 6.33 (lH,s,H-8), 12.66 (lH,s,HO-5)
MS, m/z 546 (M+,100%), 528 (14), 485 (15), 459 MS, m/z 220 (M+,100%), 205 (12),202 (14), 191
(18),445 (13),431 (I 1) (34), 190 (25), 189 (23), 161 (8),69 (9)
StL: Graphis haematites Fee Deriv: Acetyleugenitin, crystals (EtOH), mp
Lit: Mathey 1986; Mathey et al. 1994 176-17rC, by acetylation of eugenitin with
Ac 20-AcOK at 160C in 2h
3.9 StL: Mycobiont of Lecanora rupicola (L.)
Chromanes and Chromones Zahlbr.
HPLC: Rr 19
Acetyl-a-tocopherol Lit: Fox and Huneck 1969
C31Hs203 (472.75)
Eugenitol
Cll H lO 0 4 (206.19)
AcO
OH 0
Me Me
CH3ro
I I
HO ~ 0 CH 3
Crystals, mp 26.5-27.5C, [aHf + 3.03 (EtOH)
MS, m/z 472 (M+,21 %), 430 (100), 247 (2), 207 Cream-coloured prisms (EtOAc-MeOH), mp
(20), 165 (73), 121 (4) 288-289C
StL: Erioderma tomentosum Hue React: NaOCI orange
IR (KBr): 670, 690, 720, 770, 820, 850, 965, 1038, 155.93, C-1': 104.26, C-2': 76.04, C-3': 73.91, C-
1090, 1122, 1176, 1278, 1300, 1345, 1370, 1400, 4': 69.97, C-5': 73.36, C-6': 63.05, C-6' -OCO-
1492, 1562, 1620, 1642, 2800, 2950, 3150, Me: 20.37, C-6'-O~O-Me: 170.06 (a marks
3550cm-1 exchangeable values)
Deriv: Diacetyleugenitol, mp 200-202 DC, by MS, m/z 466 (M+,l%), 452 (2), 424 (6), 247 (6),
acetylation of eugenitol with Ac 20-H2S04 229 (4),220 (100), 187 (5), 109 (8)
StL: Mycobiont of Lecanora rupicola (1.)
Zahlbr.
CD(MeOH):
HPLC: RI 8
Lit: Fox and Huneck 1969 [a] x 10-3
2
Galapagin o+--r--f-+---=__
-2
C22H260n (466.43) -4
+----,-----,-
11 200 250 300nm
Me
StL: Roccella galapagoensis Follm.
H~~O HPLC: RI 5
MC: Figs. 50CD, 51A
OAe
Lit: Huneck 1972b; Huneck et al. 1992a
Pale yellowish needles (MeOH), mp 163-165 DC

React: KOH yellow, FeCl3 (EtOH) ink-blue, on Lepraric acid (Leprarsaure)
dilution with HP blue-green CIsHISOS (362.32)
UV (MeOH): 212 (4.08),231 (4.09),245 (4.10), S
255 (4.11), 285 (3.70), 335nm (3.51); MeOH +
AICI3: 214 (4.30), S 232 (4.09), S 258 (4.20), 271
(4.24), 306 (3.82), 385 nm (3.65)
IR (KBr): 746, 774, 788, 803, 837, 850, 886, 912,
936, 970, 1015, 1040, 1064, 1080, 1124, 1132,
1150, 1190, 1205, 1230, 1274, 1300, 1334, 1380, Prisms (MeOH), mp 158-160 DC
1410, 1448, 1575, 1620, 1652, 1738, 2900, React: KOH yellow, NaOH + NaOCI green, FeCl3
3340cm-1 (EtOH) red, rapidly turning green
IH-NMR (400MHz,DMSO-d6): 1.89 (3H,s,AcO- UV.(MeOH): 209 (4.35), 232 (4.39), 247 (4.30),
6'),2.12 (3H,s,Me-ll), 2.16 (3H,s,Me-12), 2.42 257 (4.30), 292 (3.80), inflexion 313 nm (3.58)
(3H,s,Me-l), 3.18 (IH,ddd,J=7.5Hz,H-1'), 3.25 IR (KBr): 705, 726, 746, 775, 790, 818, 844, 868,
(lH,ddd,J=4.5Hz,H-3'), 3.30 (lH,m,H-5'), 3.34 902,934,962,992, 1040, 1090, 1135, 1170, 1220,
(lH,m,H-2'), 4.11 (2H,m,-CH2-6'), 4.64 (lH, 1275, 1300, 1340, 1380, 1400, 1450, 1490, 1550,
d,J=7.5Hz,H-1'), 5.21 (lH,d,J=9.5Hz,HO-3'), 1620, 1650, 1720,2600,2700,3000, 3400cm-1
5.26 (lH,d,J=9.5Hz,HO-4'), 5.68 (lH,d,J= IH-NMR (100MHz,CDCI3 ): 2.27 (3H,s,Me-l),
9.5Hz,HO-2'), 6.27 (lH,s,H-3), 12.92 (IH,s, 2.38 (3H,s,Me-6'), 3.15 (2H,s,-CH 2-4'), 3.91
HO-5) (3H,s,MeO-), 5.29 (2H,s,-CH 2-9), 5.82 (lH,m,
13C-NMR (67.9MHz,DMSO-d6): C-1: 8.84, C-2: H-2'), 6.12 (lH,s,H-3), 6.41 (lH,s,H-8)
168.44, C-3: 108.04, C-4: 182.67, C-5: 152.56", MS, m/z 362 (M+,1 %), 235 (8)~; 220 (11),219 (12),
C-6: 109.70, C-7: 158.51", C-8: 114.31, C-9: 191 (3), 190 (3), 189 (3), 126 (100), 108 (11), 100
(10),98 (72),82 (12), 70 (14),67 (11),61 (13),53 MC: Fig. SIC

(22), 43 (99) Lit: Huneck 1972; Huneck et al. 1992a
Deriv: Methyl leprarate, prisms (MeOH), mp
132-133C, from lepraric acid with CH2N 2
2-Methyl-5-hydroxy-6-hydroxymethyl-7-
StL: Lepraria latebrarum (Ach.) Arnold,
methoxychromone (2-Methyl-5-
Roccella fuciformis (L.) DC.
hydroxymethyl-7 -methoxychromon)
TLC: A: 25, B: 11, B': 8, C: 24
HPLC: RJ 10 C12H 120 S (236.22)
MC: Fig. SIB
Lit: Aberhart et al. 1969
Lobodirin
C23H26012 (494.44)
Pale yellowish needles (CH 2Cl2-MeOH), mp
OH 0 198-199C
~
React: FeCl3 (EtOH) violet-red
3' OAc l' 731 UV (MeOH): 214 (4.21), 234 (4.24), 253 (4.24),
ACO~O
HO 5' 0
8 0 Me 260 (4.24), 295nm (3.89)
IR (KBr): 550, 575, 600, 625, 660, 680, 800, 820,
41
6' Me
AcO 9 880, 975, 1025, 1100, 1140, 1210, 1300, 1350,
1410, 1460, 1500, 1585, 1630, 1675, 2800,
Needles (CH 2Cl2-MeOH), mp 247-249C, [an4 3450cm-1
- 63 (EtOH: pyridine = 3: 1, v/v, c 0.74) IH-NMR (100 MHz,DMSO-d6): 2.61 (3H,s,Me-
React: KOH yellowish, FeCl3 (EtOH) ink-blue 1), 4.11 (3H,s,MeO-), 4.70 (2H,bs,-CH 2-OH),
UV (MeOH): 209 (4.27), 228 (4.36), 243 (4.43), 6.47 (lH,s,H-3), 6.88 (IH,s,H-8)
252 (4.49),259 (4.49), S 286 (3.74), 327nm (3.77) MS, m/z 236 (M+,1000/0), 235 (45),221 (30),219
IR (KBr): 850,918,1045,1080,1118,1140,1175, (48), 207 (58), 190 (34)
1220, 1230, 1270, 1310, 1330, 1380, 1400, 1430, StL: Roccella fuciformis (L.) DC.
1500, 1600, 1620, 1658, 1720, 1745, 3000, HPLC: RJ 5
3550cm-1 Lit: Huneck 1972a
IH-NMR (400MHz,CDCl3 ): 2.07 (3H,s,C-2'-
OAc), 2.09 (3H,s,C-3'-OAc), 2.14 (3H,s,C-6'- Mollin
OAc), 2.16 (3H,s,Me-8), 2.39 (3H,s,Me-l), 3.07
(IH,d,J=9.5Hz,HO-4'), 3.67' (1H,ddd,J=9.5Hz,
H-4') , 3.74 (IH,ddd,J=9.5Hz,H-5'), 4.38, 4.54
(2H,dd,J=12Hz,-CH 2-6'), 5.14 (IH,dd,J=9.5Hz,
H-3'), 5.31 (lH,dd,J=9.5Hz,H-2'), 6.05 (1H,s,H- 9~O
Me 6 510 3
3),6.48 (lH,s,H-6), 12.67 (IH,s,HO-5) 7 1
MS, m/z 494 (M+,100/0), 452 (1), 331 (3),289 (80), , o 8 11 0 Me
230 (25), 229 (100), 207 (75), 206 (100), 187 (75), 11
177 (50), 169 (75) HO ,OAe
2
Deriv: Acetyllobodirin, needles (MeOH), mp
172-173C, from lobodirin with Ac20-H2S04
StL: Roccellina cerebriformis (Mont.) Tehler.
Faint yellowish needles (acetone), mp 270- StL: Siphula ceratites (Wahlenb.) Fr.
271 c (dec.) Lit: Shimada et aI. 1980a
React: KOH yellow, FeC13 (EtOH) violet
IH-NMR (250MHz,DMSO-d6 ): 1.89 (3H,s,C-2'-
Protosiphulin
OAc), 2.03 (3H,s,Me-6), 2.39 (3H,s,Me-1), 3.28
(lH,ddd,J=9.5Hz,H-4'), 3.50 (2H,m,H-5',H-6'), C24H2S0S (444.46)
3.53 (lH,m,H-3'), 3.75 (I H,dd,J=5Hz,H-6') ,
4.73 (lH,dd,J=5Hz,HO-6'), 4.87 (lH,dd,J=
7.5Hz,H-2'), 5.32 (lH,d,J=7.5Hz,H-1'), 5.35
(lH,d,J=9.5Hz,HO-4'), 5.45 (lH,d,J=5Hz,HO-
3'), 6.27 (lH,s,H-3), 6.76 (lH,s,H-8)
13C-NMR (62.76MHz,DMSO-d 6 ): C-1: 6.92, C-2:
168.39, C-3: 108.37, C-4: 182.27, C-5: 158.13, C-
6: 108.51, C-7: 155.55, C-8: 97.72\ C-9: 19.88,
C-10: 105.00, C-11: 160.28, C-1': 93.10', C-2':
77.34, C-3': 74.54, C-4': 69.74, C-5': 73.31, C-6':
60.51, C-2'-OCOMe: 20.69, C-2'-O.GOMe: Needles (acetone-n-hexane), mp 179-182C
169.59; a marks exchangeable values (dec.), [a]D 0
Deriv: Mollin yields on acetylation with Ac20- React: FeC13 reddish purple, NaOCl red
H 2S04 acetylroccellin of mp 208-209C UV (EtOH): 230 (4.41), 278nm (4.41)
StL: Roccellaria mollis (Hampe) Zahlbr. IR (KBr): 1603, 1635, 1650, 1655, 1663,
Lit: Huneck 1972; Huneck et aI. 1992a 3300cm-1
IH-NMR (100MHz,acetone-d6): 0.89 (3H,t,Me-
Oxysiphulin 15), 1.3 [10H,m,-(CH2)s-]' 3.00 (2H,d,J=16Hz,
H-3), 3.1 (2H,t,J=8Hz,-CH2-9), 3.32 (lH,d,J=
C24H260S (442.45) 16Hz,H-3), 3.45 (2H,s,-CH 2-1), 6.11 (lH,d,H-6
or H-8), 6.28 (lH,d,H-6 or H-8), 6.40 (lH,d,H-
2' or H-4'), 6.42 (lH,d,H-2' or H-4'), 9.4, 10.8
(2x1H,2xs,2x-OH)
13C-NMR (acetone-d6): C-1: 37.2, C-2: 100.4, C-
3: 47.9, C-4: 183.4, C-9: 35.6, C-15: 14.2, C-1':
R=H,OH 149.5
MS, m/z 382, 339, 325, 311 (100%)
StL: Siphula ceratites (Wahlenb.) Fr.
Lit: Shimada et al. 1980a
Needles (acetone-H20), mp 176-178C (dec.)
React: FeC13 greyish purple
UV (EtOH): S 233 (4.46), 290nm (4.18) Roccellin
IH-NMR (lOOMHz,acetone-d6 ): 0.83 (3H,t,Me-
15), 1.3 [10H,m,-(CH2)s-]' 3.31 (2H,t,-CH 2-9),
4.42 (2H,s,-CH 2-1), 5.67 (lH,s,H-3), 6.30
(lH,d,J=2Hz,H-6 or H-8), 6.38 (lH,d,J=2Hz,H-
6 or H-8), 6.72 (lH,s,H-2' or 4')
MS, m/z 398, 355, 341, 327 (100%),313
m
9 H StL: Roccellaria mollis (Hampe) Zahlbr.

Me 10 3 HPLC: RI 8
721 MC: Figs. 51D, 52A
o 11 0
8
Me Lit: Huneck 1972; Huneck et al. I992a
AcO Siphulin
C24 H260 7 (426.45)
Cream-coloured needles (EtOAc), mp 206-

207C, [am - 62.7 (EtOH: pyridine = 3: 1, VIV, c
1.02)
React: KOH yellow, FeCl3 (EtOH) blue-violet
UV (MeOH): 210 (4.48),230 (4.39), S 243 (4.33),
C02H
252 (4.37), S 258 (4.36),286 (4.02),322 nm (3.74);
MeOH + AICI3: 212 (4.65), S 230 (4.38), S 255 Crystals (Et 2 0 or MeOH), mp about 185C
(4.39),267 (4.43), 306 (4.14), 375nm (3.81) (dec.), resolidifying and remelting about 228-
IR (KBr): 702, 750, 778, 790, 808, 858, 890, 918, 229C
964, 990, 1064, 1080, 1130, 1158, 1162, 1184, React: FeCl3 violet, Gibbs reagent blue, NaOCI
1200, 1230, 1250, 1270, 1300, 1318, 1335, 1378, red
1410, 1450, 1490, 1508, 1575, 1620, 1650, 1720, UV (EtOH): S 242.5 (4.47),251 (4.46),264 (4.32),
2950, 3420 cm-1 293 nm (4.36)
IH-NMR (400MHz,DMSO-d6 ): 1.90 (3H,s,C-6'- IR (KBr): 1617, 1635, 3300cm-1
OAc), 2.08 (3H,s,C-2'-OAc), 2.11 (3H,s,Me-9), IH-NMR (100MHz,acetone-d6 ): 0.86 (3H,t,Me-
2.38 (3H,s,Me-I), 3.30 (IH,ddd,J=9.5Hz,H-4'), 15), 1.3 [10H,m,-(CH2 )s-]' 3.16 (2H,t,J=8Hz,-
3.55 (IH,J=9.5Hz,H-3'), 3.84 (IH,ddd,J=9.5Hz, CH 2-9), 4.26 (2H,s,-CH 2-I), 5.74 (IH,s,H-3),
H-5'), 4.08, 4.38 (2H,2xd,J=5Hz,-CH 2-6'), 4.88 6.33 (IH,d,J=2Hz,H-6 or H-8), 6.42 (IH,d,J
(IH,dd,J=7.5Hz,H-2'), 5.30 (IH,d,J=7.5Hz,H- =2Hz,H-6 or H-8), 6.66 (2H,s,H-2',H-4')
I'), 5.56 (IH,d,J=5Hz,HO-3'), 5.61 (IH,d,HO- !3C-NMR (acetone-d6 ): C-l: 40.4, C-3: 116.9, C-
4'), 6.26 (IH,s,H-3), 6.74 (IH,s,H-8) 4: 179.9, C-9: 35.7, C-I5: 14.2, C-l': 148.1
MS, m/z 452 (M+,50/0) 410 (1), 368 (5), 247 (20), MS, m/z 382, 339, 325, 311
229 (20),206 (75), 187 (I5), 177 (I5), 169 (I2), Deriv: Triacetylsiphulin, mp I45-I46C (ac-
127 (40), 109 (22),42 (IOO) , etone), from siphulin with Ac 2 0-H2 S0 4
Deriv: Acetylroccellin, needles (MeOH), mp StL: Siphula ceratites (Wahlenb.) Fr.
208-209C, from roccellin with Ac 20-H2S04 TLC: A: 14, B: 27, C: 4
CD of roccellin (in MeOH): HPLC: RI22
Lit: Shimada et al. I980a; A. Kjaer and D. Kjaer
1982, 1985
[aJ x 10-3
=~1~
V:=--==--, Sordidone (Sordidon)
200 250 300nm Cl1 H 9CI0 4 (240.63)
Yellow needles (MeOH), mp 268-269, 283-

285C (EtOAc)
React: NaOCI orange-red, FeCl3 (EtOH) violet-
brown
UV (MeOH): 209 (4.32),252 (4.40), S 284 (4.00),
323 (4.00), 353nm (4.00); MeOH+AlCI3 : 209
Cream-coloured needles (MeOH), mp 265-
(4.62), 253 (4.62), S 276 (4.52), 3S0 (4.S2), S
266C
400nm (4.32)
React: NaOCI orange, FeCl3 (EtOH) blue-green,
IR (KBr): 728, 746, 784, 870, 884, 1008, 1040,
NaOH + HzO z bluish
1062, 1116, 1170, 1200, 1244, 1270, 1312, l346,
UV (EtOH): 263 (4.20),296 (3.76), 332nm (3.56)
1410, 1450, 1468, 1498, 1560, 1584, 1630, 2950,
IR (KBr): 690, 750, 780, 820, 850, 890, 975, 1008,
3S00cm-1
1030, 1l05, 1125, 1190, 1230, l300, l345, 1410,
IH-NMR (270MHz,acetone-d6 ): 2.73 (3H,s,
1440,1480,1580,1615, 1650, 3150cm-1
Me-), 6.88 (IH,s,H-7), 10.10 (2H,s,HO-3,HO-
IH-NMR (60HMz,DMSO-~): 2.03 (3H,s,Me-9),
6), 13.88 (lH,s,HO-1)
2.38 (3H,s,Me-l), 6.17 (lH,s,H-3), 9.95 (lH,bs,
I3C-NMR (25.05MHz,DMSO-d6 ): C-1: 156.1, C-
HO-7), 13.60 (IH,bs,HO-5)
2: 103.1, C-3: IS5.9, C-4: 98.5, C-S: 105.0, C-6:
MS, m/z 242 (M+,340/0), 241 (28), 240 (100), 223
158.8, C-7: 115.7, C-8: 140.1, C-9: 180.1, C-I0:
(3),222 (2), 213 (4),212 (3),211 (10),205 (5),200
22.4, C-ll: 1l0.6, C-12: 153.2, C-13: 149.1, C-
(4),199 (3), 17l (3),120 (7),69 (4), 55 (4),43 (6)
14: 101.9
Deriv: Diacetylsordidone, prisms (MeOH-HzO),
MS, m/z 366 (M+,80/0), 364 (57), 362 (97), 360
mp 154-155C, from sordidone with AczO-
(100), 328 (27), 326 (35), 299 (l3), 297 (18), 269
H ZS0 4
(7)
StL: Lecanora rupicola (1.) Zahlbr.
Deriv: Triacetylarthothelin, needles (CHCI3-
TLC: C: 42
MeOH), mp 224-226C, by acetylation of
HPLC: R, 13
arthothelin with ACzO-H2 S0 4
MC: Fig. 52B,C,D
StL: Arthothelium pacificum Follm., Lecanora
Lit: Huneck and Santesson 1969; Devlin et al.
straminea (Wahlenb.) Ach.
1971
TLC: A: 43, B': 40, C: 37, E: 15, F: 32
HPLC: R, 35, R, (SA) 61
3.10
MC: Fig. 67C
Xanthones and bis-Xanthones Lit: Huneck and Hofie 1978; Sundholm 1978b;
Fitzpatrick et al. 1980; Elix et al. 1991d, 1995c
Arthothelin, 2,4,S-Trichloronorlichexanthone
(2,4,5-Trichlornorlichexanthon)
Asemone, 4,S,7-Trichloronorlichexanthone
C14H7Cl30s (361.56) (Asemon, 4,5,7-Trichlornor-lichexanthon)
C14H7Cl30s (361.56)
HO
3.10 Xanthones and bis-Xanthones 191
MS, m/z: 322 (37%),321 (21),320 (100),319 (7),

CI~ 291 (12),277 (14)
Deriv: Acetyl-2-chlorolichexanthone, needles
HO~O~OH (CHCI3-MeOH), mp 225-226C, by acetylation
Cl Cl of 2-chlorolichexanthone with Ac20-H2S0 4
StL.: Pertusaria persulphurata Mull.-Arg.
TLC: A: 69, B': 54, C: 70, E: 29, F: 80
Yellow needles (acetone-H 2 0), mp 308-309C
(dec.) HPLC: Rr (SA) 106
Lit: Elix et al. 1978b; Elix and Crook 1992
React: NaOCI orange-red
IH-NMR (acetone-d6 ): 2.95 (3H,s,Me-), 6.46
(lH,s,H-2), 13.41 (1H,s,HO-1) 4-Chlorolichexanthone (4-Chlorlichexanthon)
13C-NMR (DMSO-d6 ): C-1: 160.4, C-2: 98.4, C-3:
160.6, C-4: 97.2, C-5: 106.9, C-6: 154.4, C-7: CI 6H13CIO s (320.71)
120.3, C-8: 137.0, C-9: 180.0, C-10: 17.9, C-11: CH3 0 HO
~
111.2, C-12: 150.7, C-13: 151.4, C-14: 102.1
MS, m/z 366 (M+,4%), 364 (33), 362 (99), 360
(100),359 (5), 331 (5),325 (10),297 (6) CH30~OyOCH3
StL: Micarea isabellina Coppins et Kantvilas Cl
TLC: A: 47, B': 55, C: 37, E: 7, F: 20
Pale yellow needles (AcOH), mp 199-200C
HPLC: R, 37; R, (SA) 78
IR (KBr): 656, 698, 720, 794, 818, 838, 862, 908,
Lit: Sundholm 1979; Elix et al. 1990d; Elix and
920,950,988,1000,1036,1060,1110,1150,1170,
Crook 1992; Elix et al. 1995c
1200, 1222, 1270, 1306, 1358, 1390, 1442, 1458,
1496, 1564, 1592, 1612, 1640, 2900, 2960,
2-Chlorolichexanthone (2-Chlorlichexanthon) 3550cm-1
IH-NMR (100MHz,DMSO-d6-CDCI3 ): 2.80 (3H,
CI 6H13CIO s (320.71)
s,Me-), 3.93, 3.98 (2x3H, 2xs,2xMeO-), 6.57
(1H,s,H-2), 6.76, 6.89 (2H,2xd, H-5,H-7)
MS,m/z 322 (M+,39%), 321 (23), 320 (100), 291
(12), 277 (15)
Deriv: Acetyl-4-chlorolichexanthone, needles .
(CHCI3-MeOH), mp 185-234C, from 4-
chlorolichexanthone with Ac 20-H2S04
Pale yellow needles (AcOH), mp 222-223C StL: Sporopodium citrinum (Zablbr.) lix,
IR(KBr}: 678, 730, 778,800,,822, 848, 874, 930, Lumbsch et Lucking
958, 992, 1040, 1064, 1094, 1106, 1150, 1174, TLC: A: 75, B': 68, C: 78, E: 59, F: 88
1210, 1280, 1310, 1340, 1360, 1400, 1438, 1460, HPLC: Rr: 50
1500, 1564, 1596, 1610, 1630, 2900, 3000, 3150, Lit: Elix et al. 1978b; Elix and Ernst-Russell 1993;
3550 cm-l Elix et al. 1995c
IH-NMR (l00MHz,DMSO-d6-CDCI3 ): 2.79 (3H,
s,Me-), 3.92,4.00 (2x3H,2xs,2x-MeO-), 6.69
5-Chlorolichexanthone (5-Chlorlichexanthon)
(1H,s,H-4), 6.80,s.88 (2H,2xd,J=2.5Hz,H-5,
H-7) CI 6H13CIO s (320.71)
Me 0 OH
~o~~
J:.Jl:L,CI
HO~O~OMe
CI
Yellow needles (EtOAc), mp 325C
Pale yellow needles (EtOAc), mp 156C IH-NMR (acetone-d6): 2.86 (3H,s,Me-), 4.07
IH-NMR (acetone-d6): 2.92 (3H,s,Me-), 3.97, (3H,s,MeO-), 6.36 (1H,s,H-4), 6.72, 6.79 (2H,
4.01 (2x3H,2xs,2xMeO-), 6.32, 6.53 (2H,2xd, 2xd,J=2.4Hz,H-5,H-7)
J=2Hz,H-2,H-4), 7.06 (1H,s,H-7), 12.24 (1H,s,- MS, m/z 308 (M+,340/0), 306 (100), 277 (13),263
OH) (15),242 (14)
MS,m/z 322 (M+,280/0), 320(100), 291 (30) StL: not yet found in lichens
StL: Lecanora contractula Nyl. Lit: Elix et al. 1992b
T1C: A: 73, B': 63, C: 77, E: 53, F: 83
HPLC: RI 48; RI (SA) 155
Lit: Elix and Crook 1992; Elix et al. 1992b 2-Chloro-6-0-methylnorlichexanthone
(2-Chlor-6-0-methylnorlichexanthon)
7-Chlorolichexanthone (7 -Chlorlichexanthon) C1sH 11 CIO s (306.69)
CI6H!3CIOs (320.71)
CI~
MeoAJlOUOMe
Pale yellow needles (AcOH), mp 280-283C
Yellow crystals (acetone-cyc1ohexane), mp React: NaOCI orange
320C (dec.) IR(KBr): 650, 672, 726, 774, 828, 852, 882, 940,
IH-NMR (CDCI3 ): 3.06 (3H,s,Me-), 3.92, 4.05 968, 994, 1034, 1058, 1076, 1146, 1162, 1198,
(2x3H,2xs,2xMeO-), 6.37 (2H,bs,H-2,H-4), 1250, 1280, 1314, 1366, 1382, 1402, 1440, 1460,
6.82 (1H,s,H-5), 13.33 (1H,s,HO-) 1500,1568, 1610, 1630,3000,3140, 3550cm-1
MS, m/z 322 (M+,340/0), 321 (21), 320 (100), 291 IH-NMR (lOOMHz,DMSO-d6-CDCI3 ): 2.73 (3H,
(18) s,Me-), 3.87 (3H,s,MeO-), 6.62, 6.69 (2H,2xd,J=
TLC: A: 73, B': 61, C: 77, E: 39 2.5Hz,H-5,H-7)
HPLC: RI 52 MS, m/z: 308 (M+,380/0), 307 (20), 306 (100), 305
StL: not yet found in lichens (7), 277 (8), 263 (9)
Lit:Elix et al. 1992b Deriv: Diacetyl-2-chloro-6-0-methylnorlich-
exanthone, blades (CHCI3-MeOH), mp 207-
211 c, with softening from 202C, by
2-Chloro-3-0-methylnorlichexanthone
acetylation of 2-chloro-6-0-methylnorlich-
(2-Chloro-3-0-methylnorlichexanthon)
exanthone with Ac20-H2 S04
C1sHllCIO s (306.69) StL: Pertusaria persulphurata Miill.-Arg.
TLC: A: 56, B': 53, C: 46, E: 20, F: 67
HPLC: Rj 31; Rj (SA) 65
4-Chloro-3-0-methylnorlichexanthone,
Griseoxanthone B (4-Chloro-3-0-
methylnorlichexanthon, Griseoxanthon B)
C1sHllCIO s (306.69)
m
CH30~OyOH
C\
Pale yellow prisms (acetone), mp 232-235C

(with softening and conversion to needles from
ca. 190C)
React: NaOCI orange
HO OMe IR (KBr): 650, 690, 830, 912, 960, 990,1030,1050,
1084, 1104, 1148, 1180, 1196, 1218, 1270, 1300,
1350, 1380, 1414, 1432, 1454, 1496, 1562, 1604,
Crystals (acetone), mp 249-250C
1640, 3000, 3500cm-1
UV (EtOH): 240 (4.51), 253 (4.34), 271 (4.02),
IH-NMR (I00MHz,DMSO-d6-CDCI3 ): 2.77 (3H,
310 (4.23), 350nm (4.02)
s,Me-), 3.92 (3H,s,MeO-), 6.32 (IH,s,H-2), 6.74,
IR (KBr): 1606, 1619, 1649cm-1
6.85 (2H,2xd,H-5,H-7).
IH-NMR (60MHz,acetone-d6 ): 2.79 (3H,m,Me-
MS, m/z: 308 (M+,430/0), 307 (24), 306 (100), 305
10), 4.03 (3H,s,MeO-), 6.52 (IH,s,H-2), 6.74
(8),277 (9),263 (14).
(IH,m,H-7), 6.81 (IH,m,H-5), 13.58 (IH,s,OH)
Deriv: Diacetyl-4-chloro-6-0-methylnorliche-
13C-NMR (25.05MHz,DMSO-d6 ): C-l: 161.0, C-
xanthone, laths (CHCI3 -MeOH), mp 195-220 DC,
2: 94.4, C-3: 162.7, C-4: 97.3, C-5: 100.2, C-6:
by acetylation of 4-chloro-6-0-methylnorliche-
160.1, C-7: 116.1, C-8: 142.5, C-9: 180.6, C-IO:
xanthone with Ac20-H2S04
22.0, C-ll: 110.00, C-12: 158.1, C-13: 97.3, C-
StL: Pertusaria persulphurata Miill.Arg.
14: 102.8, -OMe: 56.2
TLC: A: 56, B': 55, C: 36, E: 30, F: 72
Deriv: 4-Chloro-l ,3,6-tri -0-methylnorlichexan-
HPLC: R] 34
thone, needles (CHCI3-MeOH), mp 234-235C,
Lit: Elix et aI. 1978b, 1995c
by methylation of 4-chloro-3-0-methylnorli-
chexanthone with dimethyl sulphate-K2C0 3 in
acetone under reflux in 8 h 5-Chloro-6-0-methylnorlichexanthone
StL: Sporopodium citrinum (Zahlbr.) Elix, (5-Chloro-6-0-methylnorlichexanthon)
Lumbsch et Lucking
C15H ll CI0 5 (306.69)
TLC: A: 54,B: 62, C: 43, E: 36, F: 75
HPLC: R] 36 Me 0 HO
Lit: Rhodes et aI. 1961; Sundholm 1978 a,b; Elix
et al. 1995c
4-Chloro-6-0-methylnorlichexanthone
M.O~OH C\
(4-Chloro-6-0-methylnorlichexanthon)
React: N aOCI orange
C1S H ll CI0 5 (306.69) MS, mlz 308, 306 (M+)
StL: Lecanora contractula Nyl.
TLC: A: 50, B': 45, C: 46, E: 31, F: 75
HPLC: RJ 32: R] (SA) 68
Lit: Elix and Crook 1992
7 -Chloro-3-0-methylnorlichexanthone 2-Chloronorlichexanthone
(7 -Chlor-3-0-methylnorlichexanthon) (2-Chlornorlichexanthon)
C1sH l1 CIO s (306.69) Cl 4H 9 CIO s (292.66)
CH3 0 HO
CI~
CH 3 0 HO
HO~OVOCH 3 HO
fltt
~
\ I
~
0 ~
CI
OH
Crystals (acetone), mp 283-284C
UV (EtOH): 241 (4.60), 254 (4.41), 266 (4.18), Yellow needles (acetone-n-hexane), mp 310-
311 (4.12),357 (4.28) 335C (dec.), 313-314.5 c (MeOH-H 20)
IR (KBr): 1595, 1643 cm-1 React: NaOCI orange-red
IH-NMR (60MHz,acetone-d6 ): 2.99 (3H,s,Me-), UV (EtOH): 244 (4.38), 270 (4.14), 316 (4.24),
3.93 (3H,s,MeO-), 6.29 (1H,d,H-2), 6.45 (1H,d, 347nm (4.14)
H-4), 6.97 (lH,s,H-5), 13.26 (lH,s,HO-1) IR (KBr): 744,764,834,860,948,986,1004,1048,
StL: not yet found in lichens 1066, 1142, 1160, 1246, 1302, 1326, 1364, 1420,
Lit: Sundholm 1978b 1450, 1500, 157~ 161~ 1640, 3000, 3150,
3500cm-1
7-Chloro-6-0-methylnorlichexanthone IH-NMR (100MHz,DMSO-d6-CDCI3 ): 2.78 (3H,
(7 -Chloro-6-0-methylnorlichexanthon) s,Me-), 6.49 (lH,s,H-4), 6.63 (2H,m,H-5,H-7);
60 MHz, acetone-d6 : 2.78 (3H,bs,Me-), 6.51 (IH,
C1sH l1 CIO s (306.69) s,H-4), 6.71 (2H,bs,H-5,H-7), 9.87 (2H,s,HO-
3,HO-6), 14.19 (IH,s,HO-1)
CI~ !3C-NMR (25.05 MHz, DMSO-d6 ): C-1: 158.2, C-

2: 101.4, C-3: 158.7, C-4: 92.2, C-5: 100.3, C-6:
162.8, C-7: 116.1, C-8: 142.6, C-9: 180.9, C-lO:
MeOA)lOU OH
22.7, C-11: 110.4, C-12: 159.8, C-13: 153.9, C-
Pale yellow crystals (acetone-cyclohexane), mp 14: 102.1
31O-312C MS, m/z 294 (M+,35%), 293 (21),292 (100),291
React: NaOCI orange (11),263 (12)
IH-NMR (DMSO-d6 ): 2.83 (3H,s,Me-), 3.99 Deriv: Triacetyl-2-chloronorlichexanthone,
3H,s,MeO-), 6.15, 6.24 (2H,2xd,J=2Hz,H-2,H- needles (CHCI3-MeOH), mp 225-22rC, by
4), 7.03 (lH,s,H-5) acetylation of 2-chloronorlichexanthone with
MS, m/z 308 (M+,35%), 307 (18),306 (100), 263 Ac2 0-H 2S04
(13) StL: Lecanora populicola (DC.) Duby;
StL: Lecanora populicola (DC.) Duby Santesson's "2-chloronorlichexanthone" is a
TLC: A: 54, B': 56, C: 36, E: 20, F: 61 mixture of 4-chloronorlichexanthone and 5-
HPLC: RJ 40; RJ (SA) 76 chloronorlichexanthone (Sundholm 1978b)
Lit: Elix and Crook 1992, Elix et al. 1992b TLC,: A: 36, B': 41, C: 19, E: 7, F: 75
HPLC: RJ 20, RJ (SA) 18
Lit: Sundholm 1978a,b; Elix et al. 1978b, 1992b;
Elix and Crook 1992
4-CbJoronorlichexanthone CH 3 0 HO
(4-Chlornorlichexanthon)
Cl 4H 9 CIOs (292.66)
~
HO~O~OH
CI
c~ 0 HO
~
HO~OyOH
Yellow needles (acetone), mp 304-305C (dec.)
IH-NMR (l00MHz,acetone-d6 ): 2.77 (3H,d,]=
CI
0.98Hz,Me-), 6.25, 6.44 (2H,dd,]=2.4Hz,H-2,H-
Yellow needles (acetone-n-hexane), mp 296- 4), 6.88 (lH,q,]=0.98Hz,H-7), 9.8, 10.0 (2x1H,
297; 288-289C (acetone-H 2 0) 2xbs,HO-3,HO-6), 13.23 (lH,bs,HO-1)
React: NaOCI orange-red 13C-NMR (DMSO-d6 ): C-1: 162.7, C-2: 98.1, C-3:
UV (EtOH): 242 (4.54), 253 (4.34), 270 (4.17), 164.6, C--4: 93.2, C-5: 104.5, C-6: 158.0, C-7:
312 (4.20), 346nm (4.10) 115.1, C-8: 139.9, C-9: 180.6, C-10: 22.9, C-ll:
IR (KBr): 660, 838, 928, 982, 1006, 1038, 1084, 111.3, C-12: 153.4, C-13: 155.8, C-14: 101.7
1l00, 1152, 1190, 1260, 1300, 1438, 1460, 1504, MS, m/z 294 (M+,34%), 292 (l00), 263 (5), 257
1574, 1600, 1618, 1640, 3000, 3450 cm- l (4),229 (2)
IH-NMR (100MHz,DMSO-d6-CDCI3 ): 2.72 (3H, StL: Lecanora straminea (Wahlenb.) Ach.
s,Me-), 6.33 (lH,s,H-2), 6.62, 6.67 (2H,2xd,H- TLC: A: 73, B': 63, C: 77, E: 53, F: 83
5,H-7) HPLC: RJ 53
13C-NMR (25.05MHz,DMSO-d6): C-1: 160.7, C- Lit: SundhoIm 1978b, 1979; Fitzpatrick et al.
2: 97.7, C-3: 159.8, C-4: 96.6, C-5: 100.3, C-6: 1980, Elix et al. 1995c
162.6, C-7: 116.2, C-8: 142.5, C-9: 180.7, C-10:
22.6, C-ll: 1l0.2, C-12: 151.3, C-13: 151.3, C- 7-CbJoronorlichexanthone
14: 102.5 (7 -Chlornorlichexanthon)
MS, m/z 294 (M+,39%), 293 (l4), 292 (100), 291
(8), 263 (8) Cl 4 H 9 CIOs (292.66)
Deriv: Triacetyl-4-chloronorlichexanthone,
needles (CHCI 3-MeOH), mp 175-177C, by CH 3 0 HO
acetylation of 4-chlornorlichexanthone with CI~-..;:::
I I
Ac 20-H zS0 4
HO ~ 0 .0 OH
StL: Lecanora straminea (Wahlenb.) Ach.
TLC: A: 38, B': 43, C: 23, E: 19 Crystals (acetone-H 2 0), mp 292-293.5, 285-
HPLC: RJ 21 286C
Lit: Elix et al. 1978b; Sundholm 1978a,b React: NaOCI orange-red
UV (MeOH): 210 (4.56),243 (4.76), S 254 (4.65),
5-Chloronorlichexanthone S 270 (4.30), 312 (4.51), S 345 nm (4.25); MeOH +
(5-Chloronorlichexanthon) AIC13 : 210 (4.78), 235 (4.79), 265 (4.77), 342
(4.76), ?92nm (4.47)
Cl 4 H 9 CIO s (292.66) IR (KBr): 700, 7l4, 770, 808, 840, 930,1000,1038,
1066, 1098, 1160, 1266, 1298, 1350, 1382, 1420,
1450, 1512, 1600, 1638, 1680, 2950, 3400 cm- 1
IH-NMR (270MHz,acetone-d6 ): 2.96 (3H,s,
MeW
Me-), 6.20, 6.30 (2H,2xd,H-2,H-4), 6.91 (lH,s,
H-5), 9.91 (2H,s,HO-3,HO-6), 13.28 (IH,s,
HO-l)
2: 97.7, C-3: 164.7, C-4: 93.1, C-5: 101.1, C-6:
158.4, C-7: 119.3, C-8: 139.2, C-9: 180.8, C-I0: OMe CI
17.9, C-11: 111.2, C-12: 156.ta, C-13: 156.3'
C-14: 102.1; the values marked by a may be Yellow crystals, mp 224-225C
exchanged IH-NMR: 2.45 (3H,s,Me-), 4.00, 4.04 (2x3H,
MS, m/z 294 (M+,64%), 292 (100), 257 (29), 229 2xs,2xMeO-), 6.64 (1H,s,H-7), 6.75, 7.62 (2H,
(14), 158 (48) 2xd,J=8.6Hz,H-2,H-3), 13.02 (1H,s,HO-)
Deriv: Triacetyl-7 -chloronorlichexanthone, MS, mlz 322 (M+,37%), 320 (100), 307 (11), 305
needles (CHCI3 -MeOH), mp 187-188C, by (53),302 (95),290 (21),287 (21), 276 (32)
acetylation of 7-chloronorlichexanthone with StL: Rinodina thiomela (Nyl.) MUll.Arg.
AC zO-H zS0 4 TLC: A: 65, B': 45, C: 53, E: 35
StL: Lecanora populicola (DC.) Duby Lit: Elix et al. 1987d; Jiang 1991; Elix et al. 1993b
TLC: A: 72, B': 61, C: 76, E: 42, F: 78
HPLC: R] 24; Rr (SA) 39 4-Dechloro-8-0-methylthiomelin, 1-Hydroxy-
Lit: Huneck and Hafie 1978; Sundholm 1978a,b; 2-chloro-5,8-dimethoxy-6-methylxanthone
Elix and Crook 1992 (4-Dechlor-8-0-methylthiomelin, 1-Hydroxy-
2-chlor-5,8-dimethoxy-6-methylxanthon)
Chlorovinetorin (Chlorvinetorin) CI 6H 13 CIO s (320.71)
Cr4 H lO CIPs (329.12)
M~CI
R R Me~O~
OMe
HO OMe
CI R Pale yellow crystals (EtOAc-n-hexane), mp '35-
R = H, H, CI 38C
IH-NMR: 2.45 (3H,s,Me-), 3.92, 4.01 (2x3H,2xs,
2xMeO-), 6.95, 7.63 (2H,2xd,J=8.6Hz,H-3,H-
Physical data unknown,
4),6.62 (lH,s,H-7), 13.72 (lH,s,HO-)
StL: Lecanora dispersa (Pers.) Sommerf.
MS, m/z 322 (M+,36%), 320 (100), 307 (18), 305
Lit: Leuckert et al. 1990a
(55), 302 (91), 290 (18), 287 (9), 276 (27)
StL: Rinodina thiomela (Nyl.) MUll.Arg.
2-Dechloro-8-0-methylthiomelin, TLC: RF A: 0.64, B: 0.39, C: 0.51, E: 0.29
1-Hydroxy-4-chloro-5,8-dimethoxy- HPLC: Rr 0.66
6-methylxanthone (2-Dechlor-8-0- Lit: Elix et al. 1987d, 1993b, Jiang 1991
methylthiomelin, I-Hydroxy-4-chlor-5,8-
dimethoxy-6-methylxanthon)
2.-Dechlorothiomelin, 1,8-Dihydroxy-4- IR (Nujol): 720, 760, 810, 1060, 1570, 1600, 1624,
chloro-5-methoxy-6-methylxanthone (2- 1655cm-1
Dechlorthiomelin, 1,8-Dihydroxy-4-chlor-5- IH-NMR: 2.41 (3H,s,Me-), 3.91 (3H,s,MeO-5),
methoxy-6-methylxanthon) 6.67 (1H,s,H-7), 7.00 (IH,d,J=8.5Hz,H-4), 7.80
(1H,d,J=8.5Hz,H-3), 12.49 (IH,s,HO-l)
C l sHlICIO s (306.69)
m
13C-NMR (CDCI3): C-l: 156.5, C-3: 137.2, C-4:
108.0, C-6: 138.0, C-7: 112.1, C-8: 156.2, C-9:
185.2, C-I0: 17.1, C-12: 142.6, C-13: 148.6, C-5-
OMe: 61.3
Me~O~ MS, m/z 308 (M+,490/0), 293 (38), 291 (100), 272
(3),257 (6), 171 (2), 154 (1)
OMe CI
StL: Rinodina thiomela (NyL) Miill.Arg.
Yellow crystals (EtOAc-n-hexane), mp 193- TLC: A: 78, B': 76, C: 83, E: 61
194C (dec.) HPLC: Rj 46
IH-NMR (CDCI3): 2.41 (3H,s,Me-l0), 4.02 (3H, Lit: Elix et aL 1987d, 1993b
s,MeO-5), 6.67 (IH,s,H-7), 6.79, 7.67 (2xlH,
2xd,J=9Hz,H-2,H-3), 11.28, 11.90 (2xIH,2xs, Demethylchodatin
2xHO-)
13C-NMR (CDCI3): C-l: 156.0, C-2: 112.3, C-3: CIsH9Cl306 (391.59)
138.1, C-5: 111.0, C-6: 137.3, C-7: 111.5, C-8:
Cl~Cl
160.2, C-9: 185.8, C-I0: 17.1, C-ll: 108.4, C-12:
143.7, C-13: 151.2, C-14: 106.5, C-5-0Me: 61.0
MS, mlz 308 (M+,140/0), 306 (39), 293 (32), 292
(17),291 (100) HO~O~OH
StL: Rinodina thiomela (Nyl.) Miill.Arg. CI OMt>
TLC: RF A: 0.79, B: 0.80 C: 0.85, E: 0.64
HPLC: R[ 1.44 Yellow crystals (EtOAc), mp 284-286C
Lit: Jiang 1991; Elix et al. 1993b React: NaOCI orange
IH-NMR (300MHz, acetone-d6): 2.97 (3H,s,-
Me), 4.07 (3H,s,-OMe)
4-Dechlorothiomelin, 1,8-Dihydroxy-2- MS, m/z 396 (M+,20/0), 394 (4), 392 (11),390 (10),
chloro-5-methoxy-6-methylxanthone (4- 377 (21), 375 (22),55 (100)
Dechlorthiomelin, 1,8-Dihydroxy-2-chlor-5- Deriv: Tri-O-acetyldemethylchodatin, mp 235-
methoxy-6-methylxanthon) 240, from demethylchodatin with Ac20-
Cl sHlICIO s (306.69) pyridine at room temperature in 23 h
StL: Lecanora pachysoma Ryan et Poelt,
OH 0 OH Lecidella chodati (Samp.) Knoph et Leuckert
Cl TLC: C:34
Lit: Elix et aL 1994a
Me
OMe 2,4-Dichlorolichexanthone
(2,4-Dichlorlichexanthon)
Fine yellow needles (CH 2CI2-n-hexane), mp
224-227, 241-243C C16H12C120s (355.17)
Yellowish needles (acetone or CHCl3-MeOH),

mp 299-300C
UV (MeOH): 214 (4.37), 251 (4.69), 279 (3.98),
317 (4.42), S 355 (3.77); MeOH + AlCl3: 215
(4.62),254 (4,69),270 (4.60), 348 (4.61), S 405nm
(4.14)
Yellowish needles (CHCI3-MeOH-AcOH), mp IR (KBr): 664, 710, 750, 812, 828, 840, 934,1012,
184-186C 1080, 1108, lBO, 1174, 1190, 1206, 1218, 1290,
React: FeCl3 red-brown 1332, 1386, 1403, 1450, 1492, 1546, 1584, 1636,
UV (MeOH): 210 (4.30),243 (4.53), 273 (4.23), 2950, 3460 cm-1
308 (4.30), 360nm (3.84); MeOH + AlCI3 : 210 IH-NMR (60MHz,pyridine-ds): 2.73 (3H,s,Me-),
(4.39), 243 (4.50), S 273 (4.31), 286 (4.32), 335 3.73, 3.78 (2x3H,2xs,2xMeO-), 6.64, 6.75 (2H,
(4.31), 412nm (3.90) 2xs,H-4,H-7)
IR (KBr): 694, 726, 770, 844, 930, 960, 998, 1046, MS, rnlz 358 (M+,500/0), 356 (90), 354 (100), 342
1108, 1160, 1204, 1244, 1260, 1282, 1302, 1362, (12),340 (17),320 (43),313 (34),311 (42),290
1390, 1424, 1454, 1496, 1566, 1590, 1610, 1630, (29), 276 (12), 254 (17), 233 (12), 199 (9), 149
2960, 3450 cm-1 (14), 127 (10)
IH-NMR (270MHz,CDCI3 ): 2.84 (3H,s,Me-), Deriv: Acetyl-2,5-dichlorolichexanthone, nee-
3.93 (3H,s,MeO-3), 4.03 (3H,s,MeO-6), 6.72 dles (CHCI3-MeOH), mp 234-235 c, by acetyla-
(1H,d,H-7), 6.82 (1H,d,H-5), 14.02 (lH,s,HO-) tion of 2,5-dichlorolichexanthone with Ac20-
MS, m/z 358 (M+,410/0), 356 (90), 354 (100), 315 H 2S04
(17),313 (44),311 (48),290 (30),277 (30),233 StL: Pertusaria aleianta Nyl.
(14) TLC: A: 73, B': 59, C: 76, E: 43, F: 80
Deriv: Acetyl-2,4-dichlorolichexanthone, nee- HPLC: RJ 50; RJ (SA) 131
dles (CHCI3-MeOH), mp 187-189C, by acetyla- Lit: Huneck and Hoffe 1978; Fitzpatrick et aI.
tion of 2,4-dichlorolichexanthone with A~O 1980
H 2S0 4
stL: Pertusaria aleianta Nyl.
2,7-Dichlorolichexanthone
TLC: A: 78, B': 76, C: 75, E: 55, F: 87
(2,7-Dichlorlichexanthon)
HPLC: Rj (SA) 198
MC: Fig. 67D C16H12Cl20s (355,17)
Lit: Huneck and Hoffe 1978; Elix and Crook 1992
Me 0 HO
2,5-Dichlorolichexanthone Cl~Cl
(2,5-Dichlorlichexantho'n)
MeOMOUOMe
CI6 H 12 CIPs (355.17)
Pale yellow microcrystals (after sublimation),
~Cl
mp, 290-293C, extremely sparingly soluble in
all common solvents
Deriv: Acetyl-2,7 -dichlorolichexanthone, nee-
MeO~O~OMe dles (benzene-n-hexane), mp 189-193C, from
CI 2,7-dichlorolichexanthone with AczO-pyridine
MS, m/z 358 (M+), 356, 354, 213 4,7-Dichlorolichexanthone

StL: L. behringii Nyl., Lecanora populicola (4,7 -Dichlorlichexanthon)
(DC.) Duby
CI6H12ClzOs (355.17)
TLC: A: 77, B': 70, C: 80, E: 24, F: 57
HPLC: RJ 53, RJ (SA) 163
Lit: Sundholm 1978b; Elix and Crook 1992 Cl
4,5-Dichlorolichexanthone MeO OMe

(4,5-Dichlorlichexanthon) Cl
CI6H12ClzOs (355.17) Pale yellow needles (dioxane), mp 274 DC

IH-NMR (CDC13 ): 3.01 (3H,s,Me-), 3.98, 4.03
Me 0 HO (2x3H,2xs,2xMeO-), 6.40 (lH,s,H-2), 6.90 (1H,
MeO~OM'
s,H-5), 13.43 (1H,s,HO-)
MS, m/z 358 (M+,12%), 356 (65), 354 (100), 327
(13), 325 (20)
CI CI StL: not yet found in lichens
Lit: Elix et al. 1992b
Yellow crystals (benzene), mp 283-283.5 DC;
silky pale yellow needles (EtOAc), mp 285-
286.5 DC 5,7-Dichlorolichexanthone
UV (MeOH): 246 (4.57), 278 (3.87), 317 (4.26), (5,7-Dichlorlichexanthon)
348 nm (3.76) CI6H12ClzOs (355.17)
IH-NMR (60MHz,CDC13 ): 2.90 (3H,s,Me-), 4.01,
Mec~~OMe
4.06 (2x3H,2xs,2xMeO-) 6.45, 6.77 (2H,2xs,H-
2,H-7)
MS, m/z 358 (M+,15%), 356 (68), 354 (100), 313
(10),311 (16),290 (10),270 (8),269 (8),267 (9),
266 (8) Cl
Deriv: 1-0-Methyl-4,5-dichlorolichexanthone,
Pale yellow crystals (EtOAc), mp 202-205 DC
amorphous powder (benzene), mp 203-207 DC
IH-NMR (CDC13 ): 3.01 (3H,s,Me-), 3.90, 4.01,
by prolonged refluxing of 4,5-dichloroliche-
(2x3H,2xs,2xMeO-), 6.36 (lH,d,J=2.3Hz,H-2),
xanthone with dimethyl sulphate and KZC0 3 in
6.49 (lH,d,J=2.4Hz,H-4), 12.95 (lH,s,HO-).
acetone
MS, m/z 358 (M+,l1 %),356 (69), 354 (100), 329
StL: Buellia glaziouana (~remp.) Mull.Arg.,
(19), 327 (11),325 (18)
Pertusaria coronata (Ach.) Th.Fr.
StL: Sporopodium flavescens (Sant.) Vezda
TLC: A: 72, B': 60, C: 76, E: 43, F: 77
TLC: RF A: 0.47, B: 0.51, C: 0.32, E: 0.13, F: 0.52
HPLC: RJ 55; RJ (SA) 185
HPLC: RJ 55
Lit: Leuckert et al. 1970; Sundholm 1978b;
Lit: Elix et al. 1992b,c
Fitzpatrick et al. 1980; Elix and Crook 1992, Elix
et al. 1995c
2,4-Dichloro-3-0-methylnorlichexanthone
(2,4-Dichlor-3-0-methylnorlichexanthon)
ClSHIOClzOs (341.14)
Lit: Huneck and Hofle 1978; Sundholm 1979;

~Cl Jiang 1991
HO~O~OMe
Cl (2,5-Dichlor-6-0-methylnorlichexanthon)
Yellow needles (EtOAc), mp 295-296C ClsHlOCl20S (341.14)
(3H,s,MeO-), 6.86, 6.92 (2H,2xd,J=1.8Hz,H-5,
H-7), 10.15 (IH,s,HO-)
MlvCI
MS, m/z 342 (M+,700/0), 340 (100), 298 (19), 297
(31),213 (13) MeO~O~OH
StL: not yet found in lichens CI
Lit: lix et al. 1992b
Yellow crystals, mp 255-25rC
2,5-Dichloro-3-0-methylnorlichexanthone IH-NMR (acetone-d6 ): 2.90 (3H,s,Me-), 4.05
(2,5-Dichlor-3-0-methylnorlichexanthon) (3H,s,MeO-), 6.67 (1H,s,H-4), 6.76 (lH,s,H-7),
13.92 (IH,s,HO-)
CisHlOCl20S (341.14) MS, m/z 344 (M+,l10/0), 342 (60),340 (100),311
(3), 305 (2),270 (2)
StL: Unnamed Dimelaena species from Western
Australia.
TLC: A: 64, B: 51, C: 51, E: 32, F: 67
OMe HPLC: RJ 36; RJ (SA) 83
Pale yellow crystals (acetone), mp 276-278, 296-

297C (sealed tube) 2,7 -Dichloro-3-0-methylnorlichexanthone
IH-NMR (100MHz,acetone-d6 ): 2.73 (3H,bs, (2,7 -Dichlor-3-0-methylnorlichexanthon)
Me-), 4.07 (3H,s,MeO-), 6.72 (IH,s,H-4), 6.87 CisHlOCl20S (341.14)
(IH,m,H-7), 13.9 (1H,s,HO-)
13C-NMR (DMSO-d6): C-l: 16004, C-2: 10204, C- Me 0 HO
3: 158.8, C-4: 90.5, C-5: 104.6, C-6: 157.2, C-7: CI~CI
115.6, C-8: 140.2, C-9: 18004, C-10: 22.9, C-11:
110.9, C-12: 15304, C-13: 153.8, C-14: 10204, C- HoMoUOMe
3-0Me: 56.9
Deriv: 2,5-Dichloro-1 ,3,6-tri -O-methylnorliche- Thin pale yellow needles (acetone-H20), mp
xanthone, needles (CHCI3-MeOH), mp 205- 262-264,297-298C (EtOAc)
206C, from 2,5-dichloro-3-0-methylnorliche- React: FeCl3 (EtOH) dirty violet
xanthone with dimethyl sulphate and K2C0 3 in IH-NMR (acetone-d6 ): 2.99 (3H,s,Me-), 4.07
acetone in 8 h under reflux (3H,s,MeO-), 6.71, 7.01 (2H,2xs,H-4,H-5)
StL: not yet found in lichens MS, m/z 342 (M+,700/0), 340 (100), 306
TLC: Rp A: 0.56, B: 0049, C: 0045, E: 0.18, F: 0.61 Deriv: Diacetyl-2, 7-dichloro-3-0-methylnorli-
HPLC: RJ 83 chexanthone, amorphous p6wder (EtOH), mp
215-21rc, from 2,7-dichloro-3-0-methylnorli- 13C-NMR (DMSO-d6): C-l: 160.8, C-2: 95.0, C-3:
chexanthone with Ac 20-pyridine 16004, C-4: 97.7, C-5: 104.9, C-6: 158.3, C-7:
StL: Lecanora contractula Nyl. 11504, C-8: 139.8, C-9: 180.6, C-10: 22.1, C-11:
TLC: A: 53, B': 51, C: 42, E: 11, F: 41 110.8, C-12: 153.1, C-13: 150.0, C-14: 10204, C-
HPLC: Rj (SA) 92 3-0Me: 56.5
Lit: Elix and Crook 1992; Elix et aI. 1992b MS, m/z 344 (M+,l1 %), 342 (64), 340 (lOO), 311
(8), 310 (5),297 (9), 276 (10)
Deriv: 4,5-Dichlorolichexanthone, mp 283-
283.5C (EtOAc), from 4,5-dichloro-3-0-meth-
(2,7 -Dichlor-6-0-methylnorlichexanthon)
ylnorlichexanthone with CH 2N2
1DX
CisHLOCl20s (341.14) StL: Lecidella carpathica Korb.
TLC: A: 57, B': 52, C: 58, E: 24, F: 50
e OH HPLC: Rj 37
CI CI Lit: Sundholm 1978b; Fitzpatrick et aI. 1980;
Leuckert et aI. 1990b; Elix et al. 1995c
MeO 0 OH
Pale yellow needles (EtOAc), mp 309-311 c
React: NaOCI orange
IH-NMR (acetone-d6 ): 2.86 (3H,s,Me-), 4.11 ClSHlOCl20S (341.14)
(3H,s,MeO-), 6.61 (lH,s,H-4), 7.12 (lH,s,H-5)
MS, m/z 344 (M+,10%), 340 (lOO), 306 (25), 160 Me 0 HO
M'O~OH
(93)
StL: Lecanora behringii Nyl.
TLC: A: 52, B': 46, C: 46, E: 12, F: 44
HPLC: Rj 46; Rj (SA) 92 CI Cl
Lit: Elix and Crook 1992; Elix et al. 1992b
Yellow crystals, mp 280-282C
React: NaOCI orange
4,5-Dichloro-3-0-methylnorlichexanthone IH-NMR (DMSO-d 6): 2.81 (3H,s,Me-), 4.03
(4,5-Dichlor-3-0-methylnorlichexanthon) (3H,s,MeO-), 6.29 (lH,s,H-2), 7.14 (lH,s,H-7),
ClsHLOCIPs (341.14) 13.08 (IH,s,HO-)
MS, m/z 344 (M+,2%), 342 (11),340 (18),309 (3),
10 299 (2),297 (3), 184 (100)
MI? 0 HO StL: Dimelaena sp.
TLC: A: 60, B': 51, C: 48, E: 30, F: 65
HO Lit: Jiang 1991; Elix et al. 1991b, 1995c; Elix and
CI Crook 1992
Yellow needles (acetone), mp 255-257C

IH-NMR (100MHz,acetone-d6 ): 2.77 (3H,d,J=
0.7Hz,Me-), 4.05 (3H,s,MeO-), 6.55 (lH,s,H-2),
6.91 (lH,q,J=0.7Hz,7-H), 13.31 (lH,s,HO-) CisHlOCl20S (341.14)
CI~ Cl~
HO~O~OMe HO~O~OMe
CI Cl
Crystals (acetone), mp 233-236, 246-247C Pale yellow crystals (EtOAc), mp 248-250C

UV (EtOH): 241 (4.59), 256 (4.35), 270 (4.19), IH-NMR (DMSO-~): 2.82 (3H,s,Me-); in
311 (3.99), 365nm (4.34) acetone-d6: 2.94 (3H,s,Me-), 3.93 (3H,s,MeO-),
IR (KBr): 1590, 1640cm-1 6.48, 6.62 (2H,2xd,J=2.1Hz,H-2,H-4), 13.63
IH-NMR (60MHz,acetone-d6 ): 2.96 (3H,s,Me-), (1H,s,HO-)
4.04 (3H,s,MeO-), 6.50 (1H,s,H-2), 7.00 (lH, MS, m/z 344 (M+,16%), 342 (73),340 (100),314
s,H-5), 13.40 (1H,s,HO-) (7), 313 (16), 312 (16), 311 (25), 310 (9)
MS, m/z 344 (M+,l1 %), 342 (68), 340 (100), 315 StL: Lecanora epibryon (Ach.) Ach. spp. broccha
(1),313 (5), 311 (9),306 (3) (Nyl.) Lumbsch
StL: not yet found in lichens TLC: A: 67, B': 67, C: 59, E: 16, F: 40
Lit: Sundholm 1978b HPLC: Rr 46; Rr (SA) 140
Lit: Elix and Jiang 1990; Jiang 1991; Elix and
Crook 1992, Elix et al. 1995c
C1sHlOCIPs (341.14) (5,7-Dichlor-6-0-methylnorlichexanthon)
ClsHlOCl20S (341.14)
CI~
MeO~O~OH
Cl
Cl~
MeO~O~OH
Yellow prisms (EtOAc-cyclohexane), mp 286- Cl
288C
React: NaOCI orange Yellow rods (acetonitrile), mp 275-278C
IH-NMR (CDCI3 ): 2.95 (3H,s,Me-), 4.10 (3H, React: NaOCI orange-red
s,MeO-), 6.20 (1H,s,H-2), 6.89 (1H,s,H-5) UV (EtOH): 245 (4.43),260 (4.29), 340nm (4.05)
MS, m/z 342 (M+,5%), 340 (9), 306 (100), 263 IR (Nujol): 1620,1639, 3370cm-1
(12),153 (13) IH-NMR (pyridine-ds): 3.02 (3H,s,Me-), 4.01
StL: not yet found in lichens (3H,s,MeO-), 6.63, 6.71 (2H,2xd,J=2Hz,H-2,H-
Lit: Elix et al. 1992b 4), 8.73 (2H,bs,2xHO-)
MS, m/z 344 (M+), 342, 341
StL: Byssoloma subdiscordans (Nyl.) P. James
5,7 -Dichloro-3-0-methylnorlichexanthone
TLC: A: 57, B': 73, C: 46, E: 38, F: 79
HPLC: Rr 45
ClsHlOCl20S (341.14) Lit: Arshad et al. 1971; Elix etal. 1995c
2,4-Dichloronorlichexanthone 2,5-Dichloronorlichexanthone
(2,4-Dichlornorlichexanthon) (2,5-Dichlornorlichexanthon)
C14HsCl20s (327.11) C14HsCl20s (327.11)
HO~:~ CI
HO:~ CI
Yellow prisms (EtOAc), mp 285-287C Yellow prismatic needles (MeOH), mp 245-247,

React: NaOCI orange-red 267-268C
UV (MeOH): 211 (4.39),247 (4.60), S 274 (4.25), React: NaOCI orange-red
318 (4.30), 350nm (4.14); MeOH + AICI3: 211 UV (MeOH): 212 (4.61),250 (4.85), 317 (4.54),
(4.62), S 238 (4.64),270 (4.56), S 283 (4.54),347 355nm (4.12); MeOH + AlCI3: 212 (4.69), 252
(4.61), 397nm (4.27) (4.77) S 270 (4.61),348 (4.67), 400nm (4.19)
IR (KBr): 730, 766, 850, 960, 990, 1010, 1040, IR (KBr): 700, 748, 824, 840, 856, 908,1006,1060,
1060, 1118, 1158, 1190, 1240, 1264, BOO, 1426, 1080, 1120, 1170, 1190, 1218, 1280, 1295, 1356,
1470, 1566, 1590, 1610,2950, 3400cm-1 1400, 1504,1588, 1632,2950, 3200, 3500cm-1
IH-NMR (270MHz,acetone-d6 ): 2.79 (3H,s, IH-NMR (270MHz,acetone-d6): 2.72 (3H,s,
Me-), 6.78 (lH,d,H-7), 6.84 (lH,d,H-5), 9.90 Me-), 6.56 (lH,s,H-4), 6.82 (lH,s,H-7), 13.90
(2H,s,HO-3,HO-6), 14.22 (lH,s,HO-1) (lH,s,HO-l)
13C-NMR (25.05MHz,DMSO-d6 ): C-1: 156.3, C- 13C-NMR (25.05MHz,DMSO-~): C-1: 158.0, C-
2: 102.7, C-3: 155.4, C-4: 98.0, C-5: 100.2, C-6: 2: 101.6, C-3: 159.9, C-4: 93.1, C-5: 100.1, C-6:
162.9, C-7: 116.5, C-8: 142.6, C-9: 180.1, C-lO: 158.4, C-7: 119.4, C-8: 139.0, C-9: 180.2, C-lO:
22.6, C-11: 109.7, C-12: 158.0, C-13: 149.2, C- 17.8, C-11: 110.5, C-12: 156.0, C-13: 153.4, C-
14: 102.1 14: 101.8
MS, m/z 330 (M+,33%), 328 (83),326 (100),308 MS, m/z 330 (M+,60%), 328 (98), 326 (100), 297
(9), 306 (38), 299 (26), 297 (33), 294 (27), 292 (55),291 (53),236 (50), 235 (30), 189 (13), 149
(49),272 (27),258 (25),213 (44), 137 (50) (15), 115 (28)
Deriv: Tri -0-methyl-2,4-dichloronorlichexan- Deriv: Triacetyl-2,5-dichloronorlichexanthone,
thone, needles (CHCI 3-MeOH), mp 193-194C, needles (CHCI3-MeOH), mp 217-219C, from
from 2,4-dichloronorlichexanthone with dim- 2,5-dichloronorlichexanthone with Ac20-H 2S04
ethyl sulphate and K2C0 3 in acetone in 7 h StL: Lecanora epibryon (Ach.) Ach. ssp. broccha
reflux (Nyl.) Lumbsch
StL: Lecanora straminea (Wahlenb.) Ach. TLC: A: 42, B': 40, C: 32, E: 9, F: 42
TLC: A: 49, B': 43, C: 30, E: 8, F: 30 HPLC: Rj 27; Rr (SA) 39
HPLC: Rj 29; Rr (SA) 48 Lit: Huneck and Hofle 1978; Sundholm 1978a,b;
Lit: Huneck and Hofle 1978; Sundholm 1978b; Elix et al. 1991 d; Elix and Crook 1992
Elix and Crook 1992
2,7 -Dichloronorlichexanthone
(2,7 -Dichlornorlichexanthon)
C!4HsCI20s (327.11)
Me 0 HO 13C-NMR (25.05 MHz,DMSO-d6 ): C-l: 160.5, C-

CI~CI 2: 98.2, C-3: 160.6, C-4: 97.2, C-5: 105.0, C-6:
158.7, C-7: 115.7, C-8: 140.0, C-9: 180.6, C-I0:
HO~OUOH 22.5, C-ll: 151.3, C-12: 153.5, C-13: 151.3, C-
14: 102.2
Yellow crystals (acetone-H20), mp 298-299 DC MS, mlz 330 (M+), 328, 326
React: NaOCI orange-red Deriv: Triacetyl-4,5-dichloronorlichexanthone,
UV (EtOH): 245 (4.59), 260 (4.38), 270 (4.16), pale yellow microcrystals (EtOAc), mp 283-
319 (4.10), 358nm (4.28) 283.5 DC, from 4,5-dichloronorlichexanthone
IR (KBr): 1593, 1641 cm- 1 with CH 2N z in Et20-acetone in 10min
IH-NMR (60MHz,acetone-d6 ): 2.99 (3H,s,Me-), StL: Lecanora straminea (Wahlenb.) Ach.
6.55 (IH,s,H-4), 6.97 (lH,s,H-5), 14.04{lH, TLC: A: 44, B': 48, C: 33, E: 14, F: 49
s,HO-l) HPLC: Rj 26; Rr (SA) 42
13C-NMR (25.05MHz,DMSO-d6 ): C-l: 158.0, C- Lit: Sundholm 1978a,b, 1979; Elix et aI. 1991d;
2: 101.6, C-3: 159.9, C-4: 93.1, C-5: 100.1, C-6: Elix and Crook 1992
158.4, C-7: 119.4, C-8: 139.0, C-9: 180.2, C-I0:
17.8, C-ll: 110.5, C-12: 156.0, C-13: 153.4, C-
14: 101.8 4,7-Dichloronorlichexanthone
MS, m/z 330 (M+,3.5%), 328 (20), 326 (30), 294 (4,7 -Dichlornorlichexanthon)
(24),292 (69),43 (100) Cl4HsCl20s (327.11)
StL: Lecanora epibryon (Ach.) Ach. ssp. broccha
H::lb}OH
(Nyl.) Lumbsch
TLC: A: 40, B: 38,C:27,E:5,F:26
HPLC: Rl 28; Rj (SA) 49
Lit: Sundholm 1978a,b; Elix et al. 1991d, 1992b;
Elix and Crook 1992 Cl
Yellow crystals (acetone-H20), mp 290-293,
4,5-Dichloronorlichexanthone 297-298 DC
(4,5-Dichlornorlichexanthon) React: NaOCI orange-red
UV (EtOH): 243 (4.57), 255 (4.37), 270 (4.25),
Cl4 H sCIPs (327.11) 313 (4.09), 360nm (4.23)
Me 0 HO IR (KBr): 1596, 1656cm-1
IH-NMR (60MHz,acetone-d6): 2.95 (3H,s,Me-),
HO~OH Cl Cl
5.34 (2H,d,HO-3,HO-6), 6.38 (IH,s,H-2), 7.01
(IH,s,H-5), 13.31 (lH,s,HO-l)
2: 97.8, C-3: 160.0, C-4: 96.7, C-5: 100.8, C-6:
Yellow prisms (benzene), mp 291-293 DC (dec.) 158.3, C-7: 119.5, C-8: 139.0, C-9: 180.1, C-I0:
React: NaOCI orange-red, FeCl3 (EtOH) violet 17.6, C-ll: 110.5, C-12: 155.6, C-13: 150.9, C-
UV (EtOH): 247 (4.38), S 267 (4.07), S 322 (3.86), 14: 101.2
359 (4.11) MS, m/z 328 (M+,0.5%), 326 (1), 294 (0.2), 292
IH-NMR (60MHz,DMSO-d6 ): 2.68 (3H,s,Me-), (0.7),45 (100)
6.37 (lH,d,H-2), 6.79 (IH,s,H-7), 13.19 (IH,s, StL: Lecanora epibryon (Ach.) Ach. ssp. broccha
HO-l) (Nyl.) Lumbsch
TLC: A: 43, B': 47, C: 32, E: 17, F: 52 TLC: RF A: 0.62, B: 0.70, C: 0.65, E: 0.46, F: 0.83
HPLC: R] 30; R] (SA) 57 HPLC: R] 1.58
Lit: Sundholm 1978a,b; Elix et al. 1991d, 1992b; Lit: Jiang 1991
Elix and Crook 1992
1,8-Dihydroxy-3,6-dimethoxyxanthone
5,7 -Dichloronorlichexanthone (I ,8-Dihydroxy-3,6-dimethoxyxanthon)
(5,7 -Dichlornorlichexanthon)
R&
C12H 12 0 6 (288.06)
Cl4H sCIps (327.11)
HO H
8 1
CI~ MeO
6
0
3
OMe
HO~O~OH Pale yellow crystals (MeOH-H 20, mp 193-
CI 194C
IH-NMR (CDCI3 ): 3.89, (6H,s,2xMeO-), 6.33,
Yellow crystals, mp 285-290C 6.39 (2x2H,2xd,J=2.56Hz, 4x arom.-H), 12.05
React: NaOCI orange (2H,s,2x-HO-)
StL: Buellia sp. from Australia, Lecanora MS, m/z 288 (M+,100%), 259 (42),245 (10), 230
epibryon (Ach.) Ach. ssp. broccha (Nyl.) (7), 216 (4), 202 (5)
Lumbsch StL: Diploschistes sp.
TLC: A: 44, B': 48, C: 33, E: 11, F: 43 TLC: RF A: 0.75, B: 0.73, C: 0.78
HPLC: R] (SA) 60 HPLC: R] 48
Lit: Elix et al. 1991d; Elix and Crook 1992 Lit: Elix et al. 1987c
1,7-Dihydroxy-2,4-dichloro-6,8- 1,5-Dimethoxy-4-chloro-6-methyl-8-
dimethylxanthone (l, 7-Dihydroxy-2,4- hydroxyxanthone (1,5-Dimethoxy-4-chlor-6-
dichlor-6,8-dimethylxanthon) methyl-8-hydroxyxanthon)
CISHlOCl204 (325.14) CI 6H13CIO s (320.71)
::~o M.~
CI OMe CI
Pale yellow crystals, mp 188-190C Yellow crystals (EtOAc), mp 222-224C

IH-NMR (CDCI3 ): 2.43, 2.38 (2x3H,2xs,2xMe-), IH-NMR (CDCI3 ): 2.39 (3H,s,Me-), 4.02, 4.04
7.28 (lH,s,H-5), 7.70 (1H,s,H-3), 13.71 (lH,s, (2x3H,ixs,2xMeO-), 6.62 (1H,s,H-7), 6.79
HO-) (lH,d,J=9Hz,H-4), 7.72 (lH,d,J=9Hz,H-3),
MS, m/z 328 (M+,11 %), 326 (66), 324 (100), 295 12.39 (1H,s,HO-)
(31) MS, m/z 322 (M+,15%), 320 (39). 306 (34), 305
StL: Rinodina thiomela (Nyl.) Mull.Arg. (100)
StL: not yet found in lichens (2H,2xd,J=10.5Hz,H-5,H-5'), 6.72, 7.63 (2x2H,

Lit: Jiang 1991 2xd,J=8.5Hz,H-3,H-4,H-3',H-4')
MS, m/z 638 (M+,22%), 620 (5),602 (3), 579 (60),
561 (15), 179 (18), 166 (62), 151 (15), 135 (100),
3,6-Di-O-methylthiophanic acid
123 (10), 107 (65), 77 (35),69 (10)
(3,6-Di -0-methylthiophansaure)
Cl6H lOCIPs (424.07)
20
Me 0 OH
CI~CI 4 10
MeOOYOMe
CI CI O+-+---~~~ o +---~_r_-.,.........-
-2
Yellow crystals (dimethylformamide) mp > -10 I--T---.---.--
315C 250 300 350 nm 250 300 350 nm
IH-NMR (DMSO-~): 3.00 (3H,s,Me-), 4.06, 4.09 ORO CD
(2x3H,2xs,2xMeO-), 12.56 (lH,s,HO-)
of ergo chrome AA
MS, mlz 428 (12%),426 (51),424 (M+,100), 422
(86) StL: Myelochroa perisidians (Nyl.) Elix et Hale,
StL: not yet found in lichens Parmelia entotheiochroa Hue
Lit: Elix et al. 1992b TLC: A: 39, B: 16, B': 13, C: 28, G: 37
Lit: Apsimon et al. 1965; C.F. Culberson 1969;
Ergochrome AA, Secalonic acid A, Entothein Howard et al. 1976
(Ergochrom AA, Secalonsaure A)
Ergochrome AB, Secalonic acid C (Ergochrom
C32H30014 (638.56) AB, Secalonsaure C)
C32H30014 (638.56)
Yellow needles (dioxarle-n-hexane), mp 246-

248C (dec.), [ano - 75 (CHCI3, c 0.326) Yellow plates (benzene-cyclohexane), mp 187-
React: FeCl3 red 189C (dec.), [an + 25 (CHCI3, c 0.298)
UV (MeOH): 247 (4.49), 340nm (4.26) React: FeCl3 (EtOH) red
IR (KBr): 755,817,866,888,905,985,1042,1060, UV (MeOH): 236 (4.27), 339nm (4.52)
1088, 1130, 1155, 1225, 1320, 1422, 1560, 1590, IR (KBr): 740, 760, 822, 860, 883, 995,1038,1058,
1605, 1730, 2930, 3480 cm-l 1085, 1128, 1160, 1220, 1315, 1360, 1425, 1560,
IH-NMR (60MHz,pyridine-ds): 1.26 (2x3H,d, 1605, 1730,2930,3530 cm-l
J=6Hz,Me-6,Me-6'), 2.0-3.2 (6H,m,-CH 2-7,- IH -NMR (60 MHz,CDC13): 1.00-1.50 (2x3H,
>
CH 2-7',H-6,H-6'), 3.59 (2x3H,s,MeOCO-), 4.19 m,Me-6,Me-6'), 2.00-3.20 (4H,m,H-6,H-7,H-

6',H-7'), 3.71, 3.73 (6H,s,2x MeOCO-), 3.89 (2H, 5), 6.47 (lH,s,H-2), 6.58, 7.23 (2H,ABq,J=
d,J=3.89Hz,H-5,H-5'), 6.52, 6.57 (2H,2xd,J=8.5, 8Hz,H-3',H-4'), 11.18 (phenol.HO-), 11.52
8.8Hz,H-3,H-3' or H-4,H-4'), 7.37, 7.40 (2H, (HO-), 13.76 (enol. HO-), 13.83 (HO-)
d,J=8.5,8.8Hz,H-3,H-3' or H-4,H-4'), 11.68, MS, m/z 680 (M+,25%), 621 (IOO), 561 (23), 501
11.84 (2H,2xs,HO-1,HO-1'), 13.77, 13.99 (2H, (9)
2xs,HO-8,HO-8') Deriv: Eumitrin Al dimethyl ether, mp 146-
MS, m/z 638 (M+), 579, 166, 135, 107 150C, by methylation of eumitrin Al with a
Deriv: 8,8'-Di -0-methylergochrome AB, yellow slight excess of CH2N 2 in Et20 at OC in 3 hand
prisms, mp 258-259C, [an - 20 (pyridine, c chromatography
3.80), by methylation of ergochrome AB with StL: Usnea bayleyi (Stirt.) Zahlbr.
excess of CH 2N 2 in CH2Cl2 at OC in 30 min TLC: A: 47, B': 22, C: 40, G: 48
TLC: A: 42, B': 17, C: 32, G: 45 Lit: Yang et al. 1973
StL: Nephromopsis ornata (Miill.Arg.) Lai
Lit: Franck et al. 1966; Yosioka et al. 1972d
Eumitrin A2
C34H340I4 (666.61)
Eumitrin AI
C34H32015 (680.60)
Yellow needles (EtOH-benzene), mp 216-,

220C, [a]D - 76.7 (dioxane)
Yellow plates (EtOH-benzene), mp 249-252C, React: FeCl3 greenish red-brown
[a]D - 52.4 (dioxane) UV (dioxane): 262 (4.17),278 (4.26),298 (4.05),
React: FeCl3 red brown 335nm (4.39)
UV (dioxane): 272 (3.99),281 (4.02),286 (4.02), IR (KBr): 1435, 1565, 1585, 1615, 1745, 1755,
334nm (4.51) 3480 cm-I
IR (KBr): 1440, 1560, 1580, 1615, 1745, 1755, IH-NMR (I00MHz,CDCI3): 1.17 (3H,d,J=6Hz,
3480 em-I Me-6'), 1.93 (3H,s,MeCOO-5), 2.13 (3H,s,Me-
IH-NMR (lOOMHz,CDCI3): 1.18 (3H,d,J=6Hz, 3), 1.50-2.97 (8H,m,-CH2-6,7,8,7'), 3.62, 3.63
Me-6'), 1.85 (3H,s,MeCOO-5), 2.07 (3H,s,Me- (2x3H,2xs,MeOCO-10,10'), 4.13 (2H,bs,HO-
3), 1.50-2.20, 2.41-2.62 (6H,m,-CH2-6,-CH2- 8,8'), 5.02 (lH,m,H-5), 6.48 (lH,s,H-2), 6.48,
7,-CH2-7'), 3.69, 3.76 (6H,2xs,MeCOO-1O, 7.63 (2H,ABq,J=8Hz,H-3',H-4')1. 11.41 (2H,s,
MeCOO-10'), 4.16 (lH,bs,H-5'), 5.35 (lH,t,H- HO-1,HO-1'), 11.58 (HO-), 13.98 (HO-)
MS, m/z 666 (M+,56%), 607 (100), 565 (35), 547 StL: Usnea bayleyi (Stirt.) Zahlbr.
(22),487 (12),469 (10),409 (6) Lit: Yang et aI. 1973
StL: Usnea bayleyi (Stirt.) Zahlbr.
TLC: A: 47, B': 22, C: 44, G: 48
1-Hydroxy-2,4-dichloro-6,8-dimethyl-7-
Lit: Yang et al. 1973
methoxyxanthone (1-Hydroxy-2,4-dichlor-6,8-
dimethyl-7-methoxyxanthon)
Eumitrin B
C16H12C1204 (339.17)
Cl
Cl
Pale yellow crystals, mp 157-158C
lH-NMR (CDCI 3): 2.45, 2.83 (2x3H,2xs,2xMe-),
3.74 (3H,s,MeO-7), 7.28 (lH,s,H-5), 7.70
(lH,s,H-3), 13.67 (1H,s,HO-)
MS, mlz 342 (M+,5%), 340 (29), 338 (48), 325
(65),323 (100)
StL: Rinodina thiomela (Nyl.) Mull.Arg.
TLC: RF A: 0.79, B: 0.88, C: 0.86, E: 0.72, F: 0.90
HPLC: R12.92
Lit: Jiang 1991; Elix et al. 1987d,1993b
Yellow prisms (EtOH-benzene), mp 238-240C, Isoarthothelin see 2,5,7-Trichloronorliche-
[a]D - 33.3 (dioxane). xanthone, p. 217
React: FeCl3 greenish red brown
UV (dioxane): 253 (3.79),275 (4.02),295 (3.72),
336nm (4.17) Lichexanthone (Lichexanthon)
IR (KBr): 1435, 1560, 1580, 1610, 1740, 1755, Cl6Hl40S (286.27)
3520cm-1
lH-NMR (l00MHz,CDCI3 ): 1.22 (3H,d,J=6Hz, o HO
Me-6'), 1.88 (3H,s,MeCOO-), 2.06 (3H,s,Me-3),
1.40-2.65,3.30 (8H,m,-CH 2-6,7,8,7'), 3.78 (6H,s,
MeOCO-10,10'), 4.17 (lH,bs,HO-8'), 5.43 (lH,
m,H-5), 6.45 (lH,s,H-2), 6.55, 7.07 (2H,ABq,J=
8Hz,H-3',H-4'), 11.39 (2H,2xs,H-1,H-1'), Straw yellow needles (MeOH), mp 189-190C
11.56 (HO-), 13.65 (HO-) React: FeCl3 (EtOH) purple; the acetic acid solu-
MS, m/z 666 (M+,25%), 607 (100), 565 (38), 547 tion gives a green fluorescence after the addition
(22),487 (24),469 (11), 409 (10) of a: drop of conc. H 2S0 4
Deriv: 2,4' ,9'-Tribromoeumitrin B, yellow IR (KBr): 758, 800, 822, 842, 870, 898, 945, 964,
plates, mp 240C, by bromination of eumitrin B 990, 1034, 1044, 1094, 1144, 1164, 1220, 1280,
with bromine water in CHCl3 in the presence of 1314, 1374, 1400, 1415, 1430, 1438, 1452, 1492,
FeCl3 at OC in 1.5 h 1508, 1568, 1610, 1640,2950, 3450cm-1
IH-NMR (60MHz,DMSO-d 6,120C): 2.87 (3H,s,

-Me-), 3.89, 3.92 (2x3H,2xs,2xMeO-), 6.29, 6.41
(2H,2xd,J=2.3Hz,H-5,H-7), 6.78 (2H,m,H-2,
~Cl
H-4), 13.21 (lH,s,HO-) Meo~OyoH
MS, m/z 286 (M+,100%), 257 (38), 243 (12), 200 Cl Cl
(9),199 (10), 129 (8), 115 (7),87 (7),67 (7), 51 (7)
Deriv: Acetyllichexanthone, needles (EtOAc), Yellow needles (EtOAc), mp 282-284C
mp 195-196C, from lichexanthone with Ac 20- React: N aOCI orange
H 2S0 4 , Lichexanthone methyl ether, leaflets IH-NMR (acetone-d6 ): 2.88 (3H,s,Me-), 4.11
(EtOH), mp 159C, from lichexanthone with (3H,s,MeO-), 7.15 (lH,s,HO-), 13.88 (lH,s,
CH3J-K2 C03 HO-)
StL: Hypotrachyna formosana (Zahlbr.) Hale, MS, mlz 378 (M+,28%), 377 (16), 376 (84), 375
Lecidella stigmatea (Ach.) Hertel et Leuckert (18),374 (100), 342 (10),340 (14),333 (13),331
HPLC: A: 72, B: 72, B': 66, C: 75, E: 52 (11)
HPLC: RI 46 StL: Dimelaena sp. from Western Australia
MC: Fig. 53A TLC:A:63,B:56,C:60,E:8,F:36
Lit: C.F. Culberson 1969; Hay and Harris 1972; HPLC: RI 48; RI (SA) 125
Sargent 1980 Lit: Elix and Bennett 1990; Elix and Crook 1992
1-Methoxy-4-chloro-5,8-dihydroxy-6- 3-0-Methylasemone, 4,5,7-Trichloro-3-0-

methylxanthone (1-Methoxy-4-chlor-5,8- methylnorlichexanthone (3-0-Methylasemon,
dihydroxy-6-methylxanthon) 4,5,7 -Trichlor-3-0-methylnorlichexanthon)
C1sHllCIO s (306.69) ClsH9C130s (375.59)
Llte Cl~
MeoY Ho~O~OMe
Cl Cl
OH Cl
Yellow needles (EtOAc), mp 285-287, 294-

Yellow crystals, mp 194-196C 295C
IH-NMR (CDCI3): 2.38 (3H,s,Me-), 4.03 (3H, IH-NMR (l00MHz,acetone-d6 ): 2.98 (3H,s,
s,MeO-), 6.62 (1H,s,H-7), 6.79 (lH,d,J=9Hz,H- Me-), 4.07 (3H,s,MeO-), 6.59 (lH,s,H-2), 13.2
2),7.69.(1H,d,J=9Hz,H-3), \1.85 (lH,s,HO-) (1H,s,HO-1)
MS mlz 308 (M+,8%), 306 (25), 294 (10), 292 13C-NMR (DMSO-d 6 ): C-1: 160.5, C-2: 95.2, C-3:
(34), 288 (29), 57 (100) 160.8, C-4: 97.6, C-5: 106.8, C-6: 154.4, C-7:
StL: not yet found in lichens 120.2, C-8: 136.7, C-9: 179.8, C-10: 17.6, C-11:
Lit: Jiang 1991 110.9, C-12: 151.2", C-13: 149.7", C-14: 102.4,
C-3-0Me: 56.6; values marked with a may be
6-0-Methylarthothelin exchanged
MS, m/z 380 (M+,4%), 378 (32), 376 (97), 374
ClsH9Cl30s (375.59) (100),373 (2), 345 (7),344 (5),331 (8),310 (10)
StL: Lecidella asema (Nyl.) Knoph et Hertel (IH,d,H-4), 6.70 (lH,m,H-7), 6.72 (lH,m,H-5),
TLC: A: 66, B': 64, C: 65, E: 11, F: 32 13.42 (lH,s,HO-l)
HPLC: RJ 51, RJ (SA) 175 13C-NMR (25.05MHz,DMSO-d6): C-l: 162.6, C-
Lit: Sundholm 1979; Jiang 1991; Elix et al. 1991d; 2: 96.3, C-3: 165.2, C-4: 91.5, C-5: 100.2, C-6:
Elix and Crook 1992; Elix et al. 1995c 162.6, C-7: 116.0, C-8: 142.5, C-9: 181.1, C-1O:
22.5, C-11: 110.6, C-12: 158.6, C-13: 156.1, C-
14: 102.8, C-3-0Me: 55.5
6-0-Methylasemone, 4,5,7-Trichloro-6-0-
StL: Lecanora vinetorum Poelt et Hun.
methylnorlichexanthone (6-0-Methylasemon,
TLC: A: 56, B': 55, C: 35, E: 29, F: 75
4,5,7 -Trichlor-6-0-methylnorlichexanthon)
HPLC: Rr (SA) 53
CIsH9Cl30s (375.59) Lit: McMaster et al. 1960; Sundholm 1978a,b;
Elix and Crook 1992
CI~ 6-0-Methylnorlichexanthone
MeO~O~OH (6-0-Methylnorlichexanthon)
CI CI C1sH 12 0 S (272.25)
Yellow needles (acetone), mp 298-300C

MS, mlz 380, 378, 376, 374 (M+)
StL: Pertusaria pycnothelia Nyl.
TLC: A: 64, B': 74, C: 49, E: 27, F: 39
HPLC: RJ (SA) 178
Yellow crystals (acetone-H20), mp 263-265C
Lit: Elix et al. 1990d; Elix and ,Crook 1992
IH-NMR (60MHz,acetone-d6): 2.79 (3H,m,
3-0-Methylnorlichexanthone, Griseoxanthone Me-), 3.94 (3H,s,MeO-), 6.20 (IH,d,H-2), 6.32
C (3-0-Methylnorlichexanthon, Griseoxanthon (IH,d,H-4), 6.73 (IH,m,H-7), 6.80 (IH,m,H-5),
C) 9.61 (IH,s,HO-3), 13.36 (IH,s,HO-l)
13C-NMR (25.05MHz,DMSO-d6): C-1: 163.0, C-
C1sH 12 0 S (272.25)
2: 97.6, C-3: 164.2, C-4: 92.8, C-5: 98.3, C-6:
162.7, C-7: 114.3, C-8: 141.9, C-9: 180.7, C-I0:
21.6, C-11: 111.7, C-12: 158.1, C-13: 156.1, C-
14: 102.2, C-6-0Me: 55.0
MS, m/z 272 (M+), 243, 229, 200
StL: not yet found in lichens
Yellowish needles (MeOH), mp 253-255C TLC: A: 50, B': 51, C: 42, E: 27
React: FeCl3 (EtOH) violet-brown Lit: Grover et al. 1956; Sundholm 1978a,b; Elix et
UV (EtOH): 242 (4.56), 269 (3.95), 309 (4.36), al. 1978b
340nm (3.84)
IR (KBr): 1655, 3300 cm-l 8-0-Methylthiomelin
IH-NMR (60MHz,acetone-d6 ): 2.78 (3H,m,
Me-), 3.92 (3H,s,MeO-), 6.27 (IH,d,H-2), 6.43 CI6H12CI20S (355.16)
StL: Lecidella meiococca (Nyl.) Leuckert et

Hertel
,0 TLC: A: 65, B': 69, C: 61, E: 3, F: 8
Me HPLC: Rr 53; Rr (SA) 246
Lit: Elix and Crook 1992; Elix et al. 1992b,
1995c
Fine yellow threads (CH2 CI2 -n-hexane), mp
219C
IR (Nujol): 720, 830, 990,1075,1135,1570,1595, 6-0-Methylthiophanic acid
1640cm-1 (6-0-Methylthiophansaure)
IH-NMR: 2.45 (3H,s,Me-l0), 4.01, 4.02 (2x3H, ClsHsCl40s (410.04)
2xs,2xMeO-), 6.67 (IH,s,H-7), 7.74 (IH,s,H-3),
13.69 (IH,s,HO-l)
13C-NMR (CDCI3 ): C-l: 156.0, C-3: 135.7, C-6: CI CI
141.3, C-7: 107.7, C-8: 157.8, C-IO: 17.1, C-5-
OMe: 61.1, C-8-0Me: 56.5 MeO OH
MS, mlz 356 (M+,53%), 354 (98), 336 (IOO), 324 CI CI
(29), 320 (37), 310 (19),302 (27),290 (10), 276
Yellow needles (benzene), mp 250-252C
(10), 205 (7), 160 (9)
React: NaOCI orange
Deriv: Acetyl-8-0-methylthiomelin, pale yellow
UV (EtOH): 250 (4.34), 268 (4.18), 293 (3.87),
prisms, mp 210C, from 8-0-methylthiomelin
320 (3.81), 372nm (3.76)
with Ac 20-pyridine IR (Nujol): 1576, 1641, 3420 cm-1
StL: Rinodina thiomela (Nyl.) Miill.Arg. IH-NMR (DMSO-d6 ): 2.78 (3H,s,Me-), 3.96
TLC: A: 66, B': 47, C: 56, E: 34
(3H,s,MeO-)
HPLC: Rl 43
StL: Micarea isabellina Coppins and Kantvilas
Lit: Elix et al. 1987d, 1993b
TLC: A: 65, B': 71, C: 60, E: 3, F: 13
HPLC: Rr 56; Rr (SA) 198
3-0-Methylthiophanic acid Lit: Arshad et al. 1971; Elix and Crook 1992
(3-0-Methylthiophansaure)
ClsHsCl40s (41O.04) Norlichexanthone (Norlichexanthon)
Cl4HlOOS (258.22)
C[~C[ CH3 0 HO
HO~O~OMe ~
HOAJlO)lAOH
CI CI
Yellow needles (MeOH-H 2 0), mp 274-276C
Yellow needles (EtOAc-cyclohexane), mp 290- React: NaOCI orange-red
292 c (dec.) UV (MeOH): 241 (4.56),311 nm (4.35)
IH-NMR (DMSO-d6 ): 2.91 (3H,s,Me-), 4.05 IR (KBr): 1585, 1615, 1629, 1663 cm-1
(3H,s,MeO-), 12.60 (1H,s,HO-) IH-NMR (100MHz,DMSO-d6 ): 2.79 (3H,s,Me-),
MS, m/z 414 (M+,12%), 412 (51),410 (100), 408 6.19 (IH,d,H-2), 6.32 (IH,d,H-4), 6.71 (2H,bs,
(86) H-5,H-7), 13.44 (IH,s,HO-l)
13C-NMR (25.05MHz,DMSO-d6): C-1: 163.2, C-

2: 97.9, C-3: 164.4, C-4: 93.3, C-5: 100.6, C-6:
162.5, C-7: 116.0, C-8: 142.7, C-9: 181.3, C-10:
22.9, C-ll: 111.0, C-12: 158.6, C-13: 156.6, C-
14: 102.2
MS, m/z 258 (M+,100%), 232 (4), 229 (18), 201
(6), 151 (4), 145 (5), 115 (6),77 (5), 69 (9) Pine yellow threads (CH 2CI2-n-hexane), mp
Deriv: Tri-O-methylnorlichexanthone, leaflets 185C
(EtOH), mp 159C, from norlichexanthone with IR (Nujol): 810, 1375, 1570, 1600, 1620,
CH 3J-K2C0 3 1660cm-1
StL: Lecanora reuteri Schaer., Lecanora IH-NMR: 2.42 (3H,s,Me-), 4.01 (3H,s,MeO-),
straminea (Wahlenb.) Ach. 6.67 (1H,s,H-7), 7.79 (1H,s,H-3), 11.10 (lH,s,
TLC: A: 35, B': 40, C: 11, E: 14 HO-8), 12.49 (lH,s,HO-l)
HPLC: RJ 15 MS, m/z 342 (M+,37%), 340 (57), 327 (73), 325
Lit: c.P. Culberson 1969; Sundholm 1978b (100),308 (8), 306 (22),293 (17),291 (56),257
(2),205 (4)
Deriv: Diacetylthiomelin, pale yellow prisms,
Northiomelin, 1,5,8-Trihydroxy-2,4-dichloro- mp 194-195C, from thiomelin with Ac20-pyri-
6-methylxanthone (1,5,8-Trihydroxy-2,4- dine; X-ray analysis of this compound
dichlor-6-methylxanthon) StL: Rinodina thiomela (Nyl.) Miill.Arg.
Cl4HsCl20s (327.11) TLC: A: 80, B': 82, C: 88, E: 73
HPLC: RJ 53
Lit: Elix et al. 1987d; Elix and Portelli 1990
~Cl
Thiophanic acid (Thiophansaure)
Me~oy
OH Cl Cl4H6C140s (396.01)
Yellow crystals (EtOAc-n-hexane), mp 212-

Cl Cl
213C
IH-NMR (acetone-d6): 2.59 (3H,s,Me-), 6.74, HO
OH
7.99 (2H,2xs,H-3,H-7), 8.18, 10.82 (2H,2xs,
C{ Cl
2xHO-), 12.60 (1H,bs,HO-)
MS, m/z 330 (M+,2%), 328 (10), 326 (17),205 (1), Yellow needles (MeOH), mp 242-243C
204 (1), 181 (1),43 (100) React: NaOCI orange, PeCl3 (EtOH) green-black
StL: Rinodina thiomela (Nyl.) Miill.Arg. UV (MeOH): 248 (4.60), 320 (4.13), 360nm
TLC:A: 69,B: 70, C: 72,E:47,P: 85 (4.22)
HPLC: RJ 0.27 IR (KBr): 670, 738, 790, 800, 830, 882, 980, 1070,
Lit: Jiang 1991; Elix et al. 1993b 1120, 1135, 1180, 1270, 1295, 1315, 1390, 1400,
1440, 1470, 1570, 1632,3300,3550, 3700cm-1
IH-NMR (60MHz,DMSO-d6): 2.78 (3H,s,Me-)
Thiomelin
13C-NMR (25.05MHz,DMSO-d6: C-1: 155.9, C-
CisHlOCl20s (341.14) 2: 103.4, C-3: 156.2, C-4: 98.5, C-5: 106.9, C-6:
154.8, C-7: 120.5, C-8: 136.9, C-9: 179.6, C-lO: Deriv: Diacetylthiophaninic acid, needles (ben-
17.7, C-ll: 110.6, C-12: 151.2, C-13: 148.6, C- zene-n-hexane), mp 159-162 DC, from thiopha-
14: 101.7 ninic acid with Ac 20-pyridine
MS, m/z 402 (M+,2%), 400 (12), 398 (50), 396 StL: Pertusaria flavicans Lamy
(100),394 (75), 361 (10),360 (6), 359 (8), 331 (5) TLC: A: 63, B: 68, B': 63, C: 60, E: 12, F: 40
Deriv: Tri-O-methylthiophanic acid, cream- HPLC: Rj (SA) 98
coloured needles (CHzClz-MeOH), mp 215- Lit: C.F. Culberson 1969; Huneck and Hofie
216 DC, from thiophanic acid with CHzN z at 1978; Elix et al. 1978b, 1991b; Elix and Crook
room temperature in 3 days. Triacetylthio- 1992
phanic acid, cream-coloured needles (CH 2CI2-
MeOH), mp 261-262 DC, from thiophanic acid
Thuringione (Thuringion)
with Ac20-H2S0 4
StL: Lecanora rupicola (L.) Zahlbr. ClsH9Cl30s (375.59)
TLC: A: 55, B: 56, B': 52, C: 49, E: 2, F: 9
MC: Fig. 53B,C
Lit: Huneck 1966b; Sundholm 1978b; Elix HO
et al. 1991d; Elix and Crook 1992; Elix et al.
Cl Cl
1995c
Yellow needles (EtOAc), mp 278-279 DC
React: FeCl3 (EtOH) brown
Thiophaninic acid (Thiophaninsaure)
UV (MeOH): 246 (4.53), 314 (4.18), 356nm
CisHlOCl20s (341.14) (4.01)
IR (KBr): 670, 720, 742, 785, 835, 855, 870, 930,
985, 1030, 1060, 1110, 1130, 1168, 1200, 1225,
Cl 1255, 1295, 1305, 1355, 1385, 143~ 1450, 1470,
1500, 1550, 1590, 1635, 2750, 2900, 2950,
OH 3500cm-1
Cl lH-NMR (60MHz,DMSO-d6 ): 2.14 (3H,s,Me-),
4.09 (3H,s,MeO-), 6.98 (lH,s,H-7)
Yellow prisms (EtOAc or dioxane), mp 278- 13C-NMR (25.05MHz,DMSO-d 6 ): C-1: 155.8, C-
279 DC, sparingly soluble in common solvents 2: 103.0, C-3: 155.9, C-4: 98.4, C-5: 105.0, C-6,
React: NaOCI orange, FeCl3 (EtOH-HP) green 158.7, C-7: 115.8, C-8: 140.0, C-9: 180.0, C-lO:
UV (EtOH): 215 (4.39),247 (4.64), S 273 (4.27), 21.3, C-ll: 110.5, C-12: 153.0, C-13: 148.6, C-
310 (4.38), 350nm (3.82) 14: 101.8
IR (KBr): 686, 735, 752, 795, 820, 840, 870, 920, MS, m/z 380 (M+,5%), 378 (32), 376 (95), 374
936,966,994,1040,1110,1150,1195,1284,1315, (100), 363 (5), 361 (10), 359 (10), 340 (7), 331
1365, 1380, 1420, 1455, 1462, 1480, 1500, 1560, (20)
1575, 1600, 1645,2900, 3350cm-1 Deriv: Diacetylthuringione, needles (acetone-
lH-NMR (DMSO-d6-CDCI3): 2.80 (3H,s,Me-), EtOH), mp 197-198 DC, from thuringione with
3.94 (3H,s,MeO-), 6.82, 6.92 AcP-H 2S0 4
(2H,2xd,7=2.5Hz,H-5,H-7) StL: Lecidella carpathica Korb.
MS, m/z 308 (M+,43%), 307 (24), 306 (100), 305 TLC: A: 53, B': 58, C: 48, E: 15, F: 35
(8),277 (9),263 (14)
HPLC: RJ 45
MC: Figs. 53D, 54A
Lit: Huneck and Santesson 1969; Sundholm
~Cl
1978b; Fitzpatrick et al. 1980; Elix et al. 1995c MeO~O~OMe
Cl Cl
2,4,5-Trichloro-3,6-di-O-
Yellowish needles (CHCl3-MeOH-AcOH), mp
acetylnorlichexanthone, Erythrommone
225-227C
(2,4,5-Trichlor-3,6-di-0-acetylnorlichexanthon,
UV (EtOH): 210 (4.06), S 247 (4.38),252 (4.39), S
Erythrommon)
278 (3.77), 320 (4.06), 360nm (3.60); MeOH +
ClsHn Cl30 7 (445.64) AlCl3: 210 (4.41), 251 (4.44), S 280 (4.33), 350
(4.33), 415nm (4.06)
IR (KBr): 748, 786, 864, 936, 970, 998, 1016, 1090,
~Cl 1108, 1142, 1178, 1190, 1218, 1262, 1302, 1386,
1426, 1450, 1466, 1500, 1580, 1630, 2950,
Me-CO-O~O~O-CO-Me 3500cm-1
Cl Cl IH-NMR (270MHz,DMSO-d6-CDCl3): 2.85
(3H,s,Me-), 4.02, 4.06 (2x3H,2xs,2xMeO-), 7.10
Yellow needles (EtOAc), mp 244-246C (lH,s,H-7), 13.60 (lH,s,HO-)
React: FeCl3 (EtOH) brown-violet MS, m/z 394 (M+'180/0), 392 (57), 390 (l00), 347
UV (MeOH): 246 (4.63), 312 (4.18), 370nm (41),345 (41)
(3.88) Deriv: Acetyl-2,4,5-trichlorolichexanthone,
IR (KBr): 674, 690, 750, 758, 790, 814, 846, 874, needles (CHCl3-MeOH), mp 202-203C, from
890, 910, 1014, 1054, 1094, 1132, 1170, 1260, 2,4,5-trichlorolichexanthone with Ac 2 0-H2 S0 4
1300, 1370, 1392, 1442, 1490, 1574, 1598, 1638, StL: Pertusaria aleianta Nyl.
1776, 3000, 3550 cm-1 TLC: A: 75, B': 65, C: 84, E: 59, F: 80
IH-NMR (l00MHz,CDCl3): 2.35, 2.41 (2x3H, HPLC: RJ (SA) 255
2xs,2xMe-CO-0-), 2.81 (3H,s,Me-), 6.94 (lH, Lit: Huneck and H6fle 1978; Fitzpatrick et al.
s,H-7) 1980; Elix and Crook 1992
MS, m/z 448 (M+,100/0), 446 (20),444 (20), 404
(30),402 (30),364 (35), 362 (l00), 360 (l00)
2,4,7 -Trichlorolichexanthone
Deriv: 1-0-Methyl-2,4,5-trichloro-3,6-di-0-
(2,4,7 -Trichlorlichexanthon)
acetylnorlichexanthone, needles (benzene),
mp 195-19rC, from 2,4,5-trichloro-3,6-di-0- C16HnCl30s (389.62)
acetylnorlichexanthone with dimethyl sul-
M':~:~'
phate-K2 C0 3 in acetone 1n 12h reflux
StL: Haematomma erythromma (Nyl.) Zahlbr.
Lit: Huneck and Follmann 1972; Huneck and
H6fle 1978
Cl
Pale, yellow crystals (EtOAc), mp 254-256C
2,4,5-Trichlorolichexanthone
(dec.)
(2,4,5-Trichlorlichexanthon)
IH-NMR (DMSO-d6): 2.84 (3H,s,Me-), 4.02
C16HnCl30s (389.62) (3H,s,MeO-), 7.10 (lH,s,H-5), 13.82 (lH,s,HO-)
MS, m/z 392 (M+,350/0), 390 (100), 388 (93), 345 MS, m/z 392 (M+,250/0), 390 (100), 388 (90), 347
(18), 75 (30) (9)
StL: not yet found in lichens StL: not yet found in lichens
Lit: Elix et al. 1992b Lit: Elix et al. 1992b
2,5,7-Trichlorolichexanthone 2,4,7-Trichloro-3-0-methylnorlichexanthone
(2,5,7 -Trichlorlichexanthon) (2,4,7 -Trichlor-3-0-methylnorlichexanthon)
C16HnC130s (389.62) CIsH9C130s (375.59)
Cl~Cl
MeO~O~OMe
CI
H:lb}:MO CI
Pale yellow crystals (EtOAc), mp 245 DC Yellow crystals, mp 257-259 DC (dec.)

IH-NMR (CDC13): 3.02 (3H,s,Me-), 4.03, 4.05 IH-NMR (acetone-d6): 2.95 (3H,s,Me-), 4.02
(2x3H,2xs,2xMeO), 6.60 (1H,s,H-4), 13.51 (1H, (3H,s,MeO-), 7.05 (1H,s,H-5), 7.44 (1H,s,HO-
bs,HO-) 6), 13.93 (1H,s,HO-1)
MS, m/z 392 (M+,330/0), 390 (100), 388 (95), 345 MS, m/z 380 (M+,30/0), 378 (21), 376 (73), 374
(16),77 (23) (77),335 (5),333 (14),331 (14),91 (100)
StL: Lecanora epibryon (Ach.) Ach.ssp. broccha StL: not yet found in lichens
(Nyl.) Lumbsch Lit: Jiang 1991
TLC: A: 87, B': 74, C: 85, E: 58, F: 90
HPLC: RI 54 2,4,7-Trichloro-6-0-methylnorlichexanthone
Lit: Elix and Crook 1992j Elix et al. 1992bj Elix (2,4,7 -Trichlor-6-0-methylnorlichexanthon)
and Ernst-Russell 1993
ClsH9C130s (375.59)
MO:lb}:~
4,5,7 -Trichlorolichexanthone
(4,5,7 -Trichlorlichexanthon)
CI6HnC130s (389.62)
Cl
Cl~ Yellow crystals (EtOAc), mp > 310 DC (dec.)

React: N aOCl orange
MeO~0Y'oMe IH-NMR (DMSO-d6): 2.78 (3H,s,Me-), 4.03
Cl CI (3H,s,MeO-), 5.58 (1H,s,HO-3), 6.95 (1H,s,H-
5), 13.7'1 (1H,s,HO-l)
Pale yellow crystals (dioxane), mp 205-210 DC MS, m/z 380 (M+,40/0), 378 (32), 376 (97), 374
IH-NMR (CDC13): 2.91 (3H,s,Me-), 3.97, 3.99 (100), 340 (10), 297 (16)
(2x3H,2xs,2xMeO-), 6.71 (1H,s,H-2), 12.90 StL: not yet found in lichens
(1H,s,HO-) Lit: Elix et al. 1992b
2,5,7-Trichloro-3-0-methylnorlichexanthone 2,4,5-Trichloronorlichexanthone, Concretin

(2,5,7 -Trichlor-3-0-methylnorlichexanthon) (2,4,5-Trichlornorlichexanthon)
ClsH9Cl30s (375.59) C14H7Cl30s (361.56)
CI~CI CI
HOyO~oMe HO OH
CI CI
Pale yellow crystals, mp 259-261 c Yellow needles (MeOH), mp 287C (dec.)

IH-NMR (DMSO-(\;): 2.91 (3H,s,Me-), 4.05 React: FeCl3 olive green, NaOCI orange
(3H,s,MeO-), 6.81 (lH,s,H-4), 7.73 (lH,s,HO- Deriv: Triacetyl-2,4,5-trichloronorlichexan-
6),13.82 (lH,s,HO-1) thone, needles (AcOH), mp 220-222C, by
MS, m/z 378 (M+,5%), 376 (19), 374 (19), 97 (20), acetylation of 2,4,5-trichloronorlichexanthone
91 (29),44 (100) with Ac 2 0-H2S04
StL: Buellia galapagona Weber, Lecanora StL: Pertusaria pseudocorallina (Lilj.) Arn.
epibryon (Ach.) Ach.ssp. broccha (Nyl) Lumbsch Lit: C.F. Culberson 1969
TLC: A: 64, B': 56, C: 56, E: 6, F: 18 Concretin should be 2,4,5-trichloronorliche-
HPLC: RJ 47; RJ (SA) 136 xanthone because the other possible isomeres
Lit: Roth et al. 1978; Jiang 1991; Elix et al. 1991d; differ in their melting points from the melting
Elix and Crook 1992; Elix et al. 1995c point of concretin
2,5,7-Trichloro-6-0-methylnorlichexanthone 2,4,7-Trichloronorlichexanthone
(2,5,7 -Trichlor-6-0-methylnorlichexanthon) (2,4,7 -Trichlornorlichexanthon)
C14H7CI30 s (361.56)
ClsH9Cl30s (375.59)
M.:~:~ CI
:~~:~ CI
Yellow crystals (EtOAc-n-hexane), mp 228-
Yellow needles (EtOAc)" mp 249-253C 229C
React: NaOCI orange-red React: NaOCI orange-red
IH-NMR (DMSO-d6 ): 2.77 (3H,s,Me-), 3.98 (3H, IH-NMR (acetone-d6 ): 2.92 (3H,s,Me-), 6.96
s,MeO-), 6.36 (lH,s,H-4), 13.99 (lH,s,HO-1) (lH,s,H-5), 8.92 (lH,s,HO-)
MS, m/z 378 (M+,33%), 376 (90),374 (l00), 331 MS, m/z 366 (M+,4%), 364 (31), 362 (94), 360
(18) (lOQ), 328 (8), 327 (6),326 (13),325 (7),297 (4)
StL: not yet found in lichens StL: Lecanora sulphurata (Ach.) Nyl.
Lit: Elix et al. 1992b TLC: A: 51, B': 50, C: 34, E: 4, F: 16
HPLC: RJ 37; RJ (SA) 75
Lit: Elix et al. 1990d; Elix and Crook 1992
2,5,7-Trichloronorlichexanthone, Tri-O-methylarthothelin
Isoarthothelin (2,5,7-Trichlornorlichexanthon)
C17H 13 CIps (403.64)
C14H7Cl30s (361.56)
CI~CI
HO~O~OH
M.O~:~. Cl Cl
CI Yellow needles (CHCI3-MeOH), mp 200-202,
212-214C
Yellow neeldes (acetone), mp 253-254C IH-NMR (CDCI3 ): 2.87 (3H,s,Me-), 4.03
React: NaOCI orange (9H,s,3xMeO-), 6.76 (1H,s,H-7)
IH-NMR (CDCI 3-DMSO-d6 ): 3.00 (3H,s,Me-), MS, m/z 408 (M+,4%), 406 (32), 404 (64), 402
6.65 (1H,s,H-4), 8.20, 11.75, 13.85 (3x1H, (66),390 (14),388 (54), 386 (96), 384 (100),370
3xs,3xHO-) (62),368 (72), 352 (78), 350 (90), 343 (45), 341
MS, m/z 366 (M+,4%), 364 (32), 362 (99), 360 (60), 309 (38), 307 (50)
(100),328 (3),326 (6), 325 (8),307 (2), 297 (4), StL: Dimelaena cf. australiensis H. Mayrh. et
269 (2) Sheard
StL: Lecanora epibryon (Ach.) Ach.ssp. broccha TLC: A: 72, B': 55, C: 66, E: 53, F: 75
(Nyl.) Lumbsch HPLC: RJ (SA) 154
TLC: A: 45, B': 44, C: 34, E: 6, F: 18 Lit: Huneck and Santessson 1969; Huneck and
HPLC: R] 36; RJ (SA) 71 H6fie 1978; Fitzpatrick et al. 1980; Elix and
Lit: Elix et al. 1990c, 1991d; Jiang 1991; Elix and Bennett 1990
Crook 1992; Elix et al. 1995c
Vinetorin, 5-Chloro-3-0-
1,5,8-Trimethoxy-2-chloro-6-methylxanthone methylnorlichexanthone
(1,5,8-Trimethoxy-2-chlor-6-methylxanthon) (5-Chlor-3-0-methylnorlichexanthon)
C17HlSCIOs (334.74) C1sHllCIO s (306.69)
M~CI
Me 0 HO
Me~O~
MeO
HO~OM. Cl
Pale yellow gum Yellowish needles (MeOH), mp 256-256.5 c
lH-NMR (CDCIJ: 2.41 (3H,s,Me-), 3.91, 3.97, React: FeCl3 (EtOH) red-brown
4.06 (3x3H,3xs,3x MeO-), 6.58 (1H,s,H-7), 7.25 UV (MeOH): 246 (4.44), 312 (4.15), 342nm
(1H,d,J=9Hz,H-4), 7.64 (1H,d,J=9Hz,H-3) (3.94) ,
MS, mlz 336 (M+,0.2%), 334 (1), 321 (0.4), 320 IR (KBr); 690, 735, 800, 825, 835,920,960, 1005,
(0.3),319 (1), 305 (0.3),304 (0.4), 57 (100) 1035, 1060, 1110, 1150, 1170, 1200, 1235, 1270,
StL: not yet found in lichens 1308, 1350, 1390, 1442, 1510, 1550, 1600, 1650,
Lit: Jiang 1991 3000, 3400 cm-1
IH-NMR (270MHz,acetone-d6): 2.78 (3H,s, C-I0: 155.0 or 161.0, C-11: 157.9, C-12: 112.9,
Me-), 3.94 (3H,s,MeO-), 6.30 (lH,d,H-2), 6.51 C-13: 112.2, C-14: 96.4, C-15: 20.7
(IH,d,H-4), 6.87(lH,s,H-7), 9,67 (lH,s,HO-6), MS, m/z 286 (M+,62%), 240 (26), 212 (l00), 184
13.13 (lH,s,HO-l) (22),155 (22),149 (21),128 (23),77 (24), 69 (40),
J3C-NMR (DMSO-d6 ): C-l: 162.3, C-2: 97.0, C-3: 44 (52)
165.3, C-4: 91.6, C-5: 104.5, C-6: 158.2, C-7: Deriv: Alectosarmentin triacetate, crystals
115.2, C-8: 140.0, C-9: 180.7, C-I0: 22.9, C-11: (acetone-MeOH), mp 210C, from alecto-
111.2, C-12: 153.4, C-13: 155.6, C-14: 102.4 sarmentin with Ac 2 0-pyridine at room tem-
MS, m/z 308 (M+), 306, 279, 277 perature in 12h. Tri-O-methylalectosarmentin,
StL: Lecanora vinetorum Poelt et Hun. needles (EtzO-n-hexane), mp 236C, from
TLC: A: 52, B': 57, C: 48, E: 29, F: 69 alectosarmentin with dimethyl sulphate-KzC0 3
HPLC: R[ 35; R] (SA) 81 under reflux in 3 h
Lit: C.F. Culberson 1969; Sundholm 1978b, 1979; StL: Alectoria sarmentosa Ach.
Huneck and Hafle 1978; Fitzpatrick et al. 1980; Lit: Gollapudi et al. 1994
Elix and Crook 1992; Elix et al. 1995c
3.11 Ascomatic acid (Ascomatsaure)

Dibenzofuranes
Alectosarmentin ME' ME'
~
6
8 '2
3
eOOH
ME'O 0 o ME'
5 4
Cream eristals (acetone-toluene), mp 242C

HO lH-NMR (acetone-d6 ): 2.82, 2.88 (2x3H,2xs,2x-
Me), 3.88, 3.92 (2x3H,2xs,2x-OMe), 6.77, 7.01
Needles (EtOH-benzene), mp 291C (2xlH,2xd,J=2.3Hz,H-5,H-7), 7.14 (IH,s,H-4)
UV (MeOH): S229 (4.50), 235 (4.51),260 (4.45), MS, m/z 300 (M+,76%), 285 (12), 268 (5), 267
295 (4.11), 305 (4.17), 329nm (3.88); MeOH + (25), 241 (6)
HCI: 227 (4.48),238 (4.49),260 (4.45), 296 (4.07), StL: Bunodophoron patagonicum (Dodge)
305 (4.16), 331 nm (3.87); MeOH + NaOH: 236 Wedin
(4.53),274 (4.31), 319 (4.13), 357nm (3.90) TLC: RF A: 0.37, B: 0.32, C: 0.45
IR (KBr): 1145, 1165, 1,205, 1285, 1335, 1425, HPLC: R] 0.30
1465, 1590, 1620, 1695, 1740, 3400cm-1 Lit: Elix et al. 1994f
IH-NMR (500MHz,DMSO-d 6 ): 2.74 (3H,s,-
Me), 6.64 (lH,d,J=1.9Hz,H-7), 6.82 (lH,bd,J= Condidymic acid (Condidymsaure)
1.9Hz,H-5), 6.92 (lH,d,J=7.0Hz,H-14), 7.11
(IH,s,H-4), 8,05 (IH,d,J=7.0Hz,-OH), 10.81 CZ4H300S (398.48)
(lH,s,-OH)
J3C-NMR (125.7MHz,DMSO-d6 ): C-l: 141.3, C-
2: 107.8, C-3: 155.0 or 161.0, C-4: 99.8, C-5: 95.5,
C-6: 157.4, C-7: 113.8, C-8: 133.6, C-9: 167.1,
3.11 Dibenzofuranes 219
Deriv: Methyl 3-0-methylschizopeltate, needles

(MeOH), mp 199-200C, from 3-0-methyl-
schizopeltic acid with CH 2N z at room tempera-
ture in 2 min
StL: Roccella hypomecha Bory
TLC: RF A: 0.34, B: 0.29, C: 0.41
HPLC: R] 14.4
Lit: Huneck et al. 1993a
Flakes (CHCI 3 -cyclohexane), mp 152-153C
IH-NMR (CDCI3 ): 0.82-1.14 (6H,m,Me-5',Me-
5"),1.19-1.96 (12H,m,-CH z-2'- -CH z-4',-CH z- Didymic acid (Didymsaure)
2"- -CH 2-4"), 3.08, 3.50 (4H,m,-CH 2-1',- C22 Hz60 S (370.43)
CH 2-1"), 3.96 (3H,s,MeO-), 6.80, 6.94 (2H,
2xd,J=2Hz,H-5,H-7), 6.98 (1H,s,H-4)
MS, m/z 399 (12%), 398 (M+,45), 381 (28), 380
(100),354 (41), 323 (5),309 (5),308 (5),298 (15),
297 (5), 281 (6),280 (6),268 (7), 267 (20),259 (5),
258 (21),255 (5),253 (5),251 (5),243 (5),241 (7),
239 (5),237 (5),211 (5), 165 (6), 152 (5),91 (5)
StL: Cladonia rigida (Hook. et Tayl.) Hampe ME'O
TLC: A: 47, B: 77, B': 74, C: 52
Lit: Chester and Elix 1981a Needles (n-hexane), mp 165-167C (dec.), 172-
173C (dec.)
3-0-Demethylschizopeltic acid React: NaOCI blue-green, FeCl3 blue
(3-0-Demethylschizopeltsaure) UV (MeOH): 243 (4.66), 249 (4.59), 256 (4.55),
262 (4.48), 310 (4.28)
ClsHl607 (344.31) IH-NMR (500MHz,acetone-d6): 0.86 (3H,t,J=
**
'0 7.3Hz,Me-5'), 1.01 (2H,t,J=7.5Hz,Me-3"), 1.33
OME' ME'
(2H,sextet,J=7.3Hz,-CHz-4'), 1.39 (2H,m,-CH 2-
8 , 2 ~OOME' 3' -), 1.66 (2H,m,-CH z-2'), 1.72 (2H,sextet,J=
" 3 7.5Hz,-CH z-2"), 3.06 (2H,m,-CH z-l"), 3.38
ME' 5 0 4 OH (2H,m,-CH 2-1'), 3.88 (3H,s,MeO-), 6.82 (1H,d,
'2 eOOH J=2.4Hz,H-7), 6.94 (1H,s,H-4), 7.00 (1H,d,
Needles (acetone-MeOH), mp 292-294C (dec.) J=2.4Hz,H-5)
IR (KBr): 602, 752, 785, 820, 835, 940, 970, 1035, 13C-NMR (125.7 MHz,acetone-d6): C-1: 139.7,
1070, 1098, 1124, 1152, 1225, 1275, 1370, 1425, C-2: 117.3, C-3: 158.7; C-4: 97.4, C-5: 95.8, C-6:
1580, 1620, 1655, 2925, 3400 cm- 1 159.5, C-7: 114.2, C-8: 138.7, C-9: 172.3, C-10:
IH-NMR (acetone-d6): 2.73 (3H,s,Me-11), 3.09 159.7, C-11: 159.2, C-12: 116.4, C-13: 117.8, C-
(3H,s,Me-10), 4.02, 4.03 (2x3H,2xs,MeO-, 1': 33.5, C-2': 32.8, C-3': 32.2, C-4': 23.2, C-5':
MeOCO-), 6.70 (1H,s,H-7), 6.91 (1H,s,HOOC-), 13.9, C-1": 39.3, C-2": 25.6, C-3": 14.3, C-6-
7.02 (1H,s,H-4), 11.11 (1H,s,HO-3) OMe: 5'5.9
MS, m/z 344 (M+,19%), 312 (100), 284 (6), 156 MS, m/z 370 (M+,21 %), 353 (25), 352 (100), 327
(8), 147 (26), 139 (9), 133 (7), 115 (7),76 (10), 69 (12), 326 (46),295 (15),280 (15),267 (12),241
(10),63 (11), 51 (11) (15)
Deriv: Acetyldidymic acid, needles (n~hexane 32.6, C-6': 23.2, C-7': 14.2, C-1": 51.0, C-2":
benzene), mp 116C, from didymic acid with 208.4, C-3": 43.0, C-4": 23.9, C-5": 32.1, C-6":
AC zO-H zS0 4 23.1, C-7": 14.3
StL: Cladonia floerkeana (Fr.) FlOrke MS, m/z 468 (M+,6%), 450 (100), 424 (20), 352
TLC: A: 44, B: 77, B': 68, C: 52 (80),334 (40), 307 (46)
HPLC: RI 35 Deriv: Triacetylhaemophaein, needles (MeOH),
MC: Figs. 47D, 48A mp 95-97C, from haemophaein with Ac2 0-
Lit: Shibata and Iitaka 1984; Carvalho and pyridine
Sargent 1984c StL: Phyllopsora haemophaea (Nyl.) Miill.Arg.
TLC: RF 0.43 (n-hexane:Et2 0:HCOOH = 30:
20: 6), 0.67 (benzene: dioxane: AcOH = 36: 10 :
Haemophaein, Furfuraceic acid
1.6)
(Furfuraceinsaure)
Lit: Himmelreich and Huneck 1994; Elix et al.
CZ7H3207 (468.53) 1994e
7/1 7'
Mf? Mf?
Hypostrepsilic acid (Hypostrepsilinsaure)
C1sH120s (272.25)
15 14
Me Me 9
~OOH
HO 5 11 0 10 4 OH
Needles (MeOH), mp 208-210C (dec.) Solid material, no mp given

React: NaOCl greenish, FeCl3 (EtOH) blue-green UV (MeOH): 241 (4.7),257 (4.5), 309nm (4.2);
UV (MeOH): 241 (4.66), S 264 (4.51), 271 (4.53), MeOH + NaOH: 208 (5.3), 239 (4.6), 320nm (4.3)
S 303 (3.96),312 (4.08), 338nm (3.80); MeOH + IR (KBr): 1600, 1635, 2900-3380 cm-1
NaOH: 241 (4.67), S 265 (4.57), 276 (4.64),287 IH-NMR (400MHz,DMSO-d 6 ): 6.60 (1H,d,J=
(4.67), S 306 (4.23), S 317 (4.14), 375nm (3.94) 2.5Hz,H-7), 6.78 (1H,d,J=2.5Hz,H-5), 6.88
IR (KBr): 533, 798, 1044, 1157, 1383, 1435, 1605, (1H,s,H-4)
1634, 1705,2853,2925, 2955cm-1 13C-NMR (22.5MHz,DMSO-d6 ): 20.9 (Me-IS),
IH-NMR (500MHz,acetone-d6 ): 0.85 (3H,t,J=6.8 24.6 (Me-14), 95.4 (C-4), 95.6 (C-5), 114.2 (C-
Hz,Me-7"); 0.92 (3H,t,J=6.8Hz, Me-7'), 1.27 (4H, 7), 114.9, 116.0, 119.5, 128.5, 131.5, 153.2, 155.8,
m,-CH2-5",-CH 2-6"), 1.37 (4H,m,-CH 2-5',-CH2- 156.1, 157.2, 169.9 (C-9)
6'), 1.56 (2H,m,-CH 2-4"); 1.57 (2H,m,-CH 2-4'), MS, m/z 272 (M+,43%), 254 (100), 228 (63), 198
2.01 (2H,m,-CH 2-3'), 2.64 (2H,m,-CH 2-3"), 3.67 (41), 169 (11), 141 (12), 115 (14)
(2H,ABq,J=16.4Hz,-CH2-1'), 6.74 (lH,d,H-7), Deriv: Methyl di-O-methylhypostrepsilate, mp
6.95 (1H,d,J=2.4Hz,H-5), 6.96 (1H,s,H-4) 156-157 C, from hypostrepsilic acid with CH 2N2
13C-NMR (125.7MHz,acetone-d6 ): C-1: 133.2, in Et2 0-MeOH in 24h
C-2: 117.3, C-3: 159.5, C-4: 98.3, C-5: 97.9, C-6: StL:' Mycobiont of Evernia esorediosa
157.9, C-7: 116.5, C-8: 131.2, C-9: 171.1, C-10: (Miill.Arg.) Du Rietz
162.2, C-ll: 161.9, C-12: 105.3, C-13: 116.4, C- TLC: RF x 100 1 norstictic acid 51/69 (benzene:
1': 38.1, C-2': 104.6, C-3': 41.4, C-4': 24.0, C-5': dioxane:HOAc = 36:9: 1), 55/40 (n-hexane:
3.11 Dibenzofurances 221
Et 20:HCOOH = 13:80:2), 35/34 (toluene: 126 (11),110 (7), 97 (8), 85 (6), 76 (13), 63 (13),
AcOH = 20:3) 57 (21)
Lit: Miyagawa et al. 1993 StL: Schizopelte californica Th.Fr.
Lit: Naidu 1993; Elix and Naidu 1995
Isodidymic acid (Isodidymsaure)
(+)- and (-)-Isousnic acid [(+)- und (-)-
C22H260S (370.43)
Iso usninsa ure ]
ClsHl607 (344.31)
Me
Needles (CH 2CI2-n-hexane), mp 148-150 DC 15
lH-NMR (CDCI3 ): 0.80-1.02 (6H,m,Me-5',Me- (+)-(12R)-Isousnic acid
3"), 1.20-1.85 (8H,m,-CH 2-2'-CH2-4',-CH2-
Me
2"),3.07 (2H,bt,-CH 2-1'), 3.50 (2H,m,-CH 2-1"),
3.90 (3H,s,-OMe), 6.78, 6.91 (2x1H, 2xd,J=2Hz,
H-5,H-7), 6.97 (1H,s,H-4), 11.00 (lH,bs,-OH) Me o
MS, m/z 370 (M+,18%), 352 (35), 326 (100)
StL: Cladonia didyma (Fee) Vain. a HO Me
TLC:A:42,B:66,C:50 (-)-(12S)-Isousnic acid
Lit: Chester et al. 1986
Yellow prisms (CH 2CI2 -MeOH), mp 150-152 DC,
Isoschizopeltic acid (Isoschizopeltsaure) [am + 490 (CHCI3 , c 0.8) respectively - 490
React: FeCl3 (EtOH) red-brown
Cl9H1S09 (358.10) UV (EtOH): 232 (4.42),282 (4.47), 327nm (3.91)
IR (KBr): 700, 775, 840, 900, 930, 955, 965, 1010,
**
14
OMe Me 9
1030, 1080, 1100, 1120, 1150, 1165, 1262, 1338,
1362, 1422, 1450, 1540, 1620, 1680, 2950, 3050,
1 eOOH
3500cm-1
16
Me 6 a 4 OMe
lH-NMR (500MHz,CDCI3 ): 1.76 (3H,s,Me-13),
2.11 (3H,s,Me-16), 2.66 (3H,s,Me-15), 2.77 (3H,
eOOMe s,Me-18), 5.95 (1H,s,H-4), 11.30 (1H,s,HO-10),
15
14.36 (lH,s,HO-8), 18.70 (1H,s,HO-3)
Needles (EtOAc-n-hexane), mp 199-201 DC MS, m/z 344 (M+,62%), 329 (12), 311 (6), 260
lH-NMR (CDCI 3 ): 2.71 (3H,s,Me-16), 2.96 (3H,s, (100),233 (83),217 (38)
Me-14), 4.06, 4.07, 4.17 (3x3H,3xs,3xMeO-), Deriv: (+)-Diacetylisousnic acid, pale yellow
6.98 (1H,s,H-7), 7.26 (1H,s,H-4) cubes (MeOH), mp 110-112 and 181-183 DC;
MS, m/z 358 (M+,100%), 343 (9), 327 (17), 325 [am + 289 (dioxane, c 0.048), from (+)-iso-usnic
(11),300 (10),269 (6), 155 (6), 140 (8),139 (11), acid with Ac 20-H2 S0 4 at room temperature in
24 h. Shaking a solution of isousnic acid in EtzO Methyl ascomatate (Ascomatsauremethylester)

with a saturated solution of copper-II-acetate in
ClsHlSOS (314.32)
HzO yields a blue-grey precipitate of an isousnic
Lc6:
acid-copper complex 15 14
StL: (+)-Isousnic aid: Cladonia mitis Sandst., ME> ME> 9
(-)-isousnic acid: Cladonia pleurota (F16rke) COOME>
Schaer. 6 3
HPLC: R] 41 ME>O 0 oME>
MC: Fig. 48B,C Cream crystals (CH 2CI 2-n-hexane), mp 154 DC
Lit: C.F. Culberson 1969; Taguchi and Shibata IH-NMR (CDCI3 ): 2.79, 2.85 (2x3H,2xs,2x-Me),
1970; Huneck et al. 1981 3.91 (6H,s,2x-OMe), 6.71, 6.91 (2xlH,2xd,J=
22.1Hz,H-5,H-7), 6.94 (1H,s,H-4)
Melacarpic acid (Melacarpsaure) MS, m/z 314 (M+,100%), 299 (17), 284 (7), 283
(28), 282 (9), 268 (7), 267 (27)
C22 Hz6 0 S (370.18)
StL: Bunodophoron patagonicum (Dodge)
7' Wedin
Me TLC: RF A: 0.67, B: 0.53, C: 0.53, E: 0.48, F: 0.86
HPLC: R] 0.42
Lit: Elix et al. 1994f
9-Methyl 4-hydroxypannarate
(4-H ydroxypannarsaure-9-methylester)
C17H I4 0 S (346.28)
5 4
Flakes (Et 20-n-hexane), mp 148-149 DC OH 9
COOME>
IH-NMR (IOOMHz,CDCIJ: 0.86 (3H,t,Me-7'),
1.08-1.94 (IOH,m,-CH z-2' -CHz-6'), 2.84 (3H, 16
ME> OH
s,Me-14), 3.63 (2H,m,-CH 2-1'), 3.87 (3H,s,
MeO-6), 6.76, 6.91 (2H,2xd,J=2Hz, H-5,H-7), 15
6.98 (IH,s,H-4)
MS, m/z 370 (M+,39%), 353 (25), 352 (IOO), 327 Buff needles (acetone-cyclohexane), mp 180-
(22), 326 (88), 267 (33), 242 (23), 241 (39), 44 181 DC
(20) IH-NMR (acetone-d6 ): 2.66 (3H,s,Me-16), 3.07
Deriv: Benzyl melacarpate, pale yellow flakes, (3H,s,Me-14), 4.07 (3H,s,-COOMe), 6.88 (1H,s,
mp 110-111 DC, from melacarpic acid with ben- H-7), 9.70 (1H,s,-OH), 9.89 (2H,s,2x-OH)
zyl bromide-KHC0 3 in dimethyl acetamide MS, m/z 346 (M+,0.2%), 314 (1), 302 (2),286 (2),
StL: Neophyllis melacarpa (Wils.) Wils. 270 (1), 257 (1), 242 (1), 205 (1), 196 (1), 183
TLC: RF 0.75 (n-hexane:EtzO:HCOOH (1),167 (1),149 (2), 139 (2), III (II), 97 (26), 91
13:8:2) (14); 83 (36),69 (53),67 (21),57 (100)
HPLC: R] 40 Deriv: 9,15-DimethyI4-hydroxypannarate, pale
Lit: Chester and Elix 1980; Carvalho and Sargent buff crystals (n-hexane-EtOAc), mp 180-182 DC
1984b StL: Leproloma diffusum Laupdon
TLC: Rp A: 0.15, C: 0.19, G: 0.21 6-0-Methylnorascomatic acid

HPLC: Rj 25.5 (6-0-Methylnorascomatsaure)
Lit: Elix et al. 1994c
Cl6Hl40S (286.27)
Methyl 6-0-methylnorascomatate
(6-0-Methylnorascomatsauremethylester) 15
Me
14
Me
C17H 1Ps (300.30) 7~~OOH

MeO~OH 5 4
15 14
~
Me Me 9
COOMe
6 3
Crystals (EtOAc-AcOH-n-hexane), mp 204C
MeO 0 OH (dec.)
IH-NMR (CDCI3 ): 2.84 (3H,s,Me-15), 3.05 (3H,
s,Me-14), 3.88 (3H,s,-OMe), 6.77, 6.99 (2x1H,
Pale yellow crystals (CH 2 CI 2 -n-hexane), mp 2xd,J=2.2Hz,H-5,H-7), 6.90 (lH,s,H-4)
147-149C MS, m/z 286 (M+,4%), 268 (14), 243 (16), 242
IH-NMR (CDCI3 ): 2.81 (3H,s,Me-14), 2.97 (3H, (100),241 (9),228 (11), 227 (71), 199 (7), 198 (7),
s,Me-15), 3.87 (3H,s,-OMe), 4.02 (3H,s,- 197 (6), 184 (10)
COOMe), 6.71, 6.87 (2xlH,2xd,J=2.5Hz,H-5,H- StL: Bunodophoron patagonicum (Dodge)
7) 6.92 (1H,s,H-4), 11.18 (1H,s,-OH). Wedin
MS, m/z 300 (M+,23%), 269 (20), 268 (100), 169 TLC: RF A: 0.39, B: 0.63, C: 0.47
(8), 168 (29), 154 (8), 150 (7), 149 (33), 139 (7), HPLC: Rj 0.35
138 (6), 137 (55) Lit: Elix et al. 1994f
Wedin
9-Methyl pannarate (Pannarsaure-9-
TLC: Rp A: 0.70, B: 0.55, C: 0.55, E: 0.60, F: 0.88
methylester)
HPLC: Rj 0.39
Lit: Elix et al. 1994f Cl7Hl407 (330.28)
**
14
OH Me
8 tOOMe
16
Me 0 OH
4
eOOH
15
Tuft needles (CHC1 3-MeOH), mp 218-220C MS, m/z 330 (M+,8%), 312 (32), 286 (100), 255
(dec.) (59),226 (40), 127 (26),44 (65)
React: NaOCl green Deriv: Dimethyl pannarate, mp 254-257C,
UV (MeOH): 247 (4.78), S 275 (4.39), S 303 from IS-methyl pannarate with CH 2N2 in ac-
(4.11), S 314nm (4.03) etone-MeOH at OC in 30 s
IR (KBr): 460, 530,570,620, 760, 790, 825, 940, StL: Leproloma vouauxii (Hue) Laundon
985, 1040, 1090, 1115, 1160, 1230, 1275, 1330, TLC: RF A: 0.23, B: 0.33, C: 0.17, G: 0.24
1375, 1430, 1450, 1590, 1650, 1675, 3370cm-1 HPLC: R[ II
IH-NMR (400MHz,acetone-d6 ): 2.53 (3H,s,Me- Lit: Laundon 1989; Leuckert and Kiimmerling
16),3.00 (3H,s,Me-14), 3.93 (3H,s,-COOMe-9), 1989; Elix et al. 1990e
6.75 (lH,s,H-4), 6.94 (lH,s,H-7), 9.90 (1H,bs,
HO-8), 10.15 (2H,bs,HO-3,-COOH-15) 3-0-Methylpannaric acid
MS, m/z 286 (M-C0 2 ,53%), 254 (100), 198 (69) (3-0-Methylpannarsaure)
Deriv: Dimethyl pannarate, mp 254-257C,
from 9-methyl pannarate with CH 2 N 2 in ac- Cl7Hl407 (330.28)
etone-MeOH at OC in 30 s
StL: Roccella capensis Follm. 14
~
TLC: RF 0.35 (n-hexane:Et2 0:HCOOH = 30: OH Me ~OOH
20 :6)
HPLC: R[ 13 16 3
Me 0 OMe
Lit: Huneck et al. 1991b; Elix et al. 1992a
eOOH
15
IS-Methyl pannarate
(Pannarsaure-15-methylester) Crystals (EtOAc-n-hexane), mp 164-166C
IH-NMR (CDC13 ): 2.67 (3H,s,Me-16), 3.05 (3H,
C17H I4 0 7 (330.28) s,Me-14), 4.06 (3H,s,MeO-3), 6.89 (1H,s,H-7),
7.28 (IH,s,H-4)
MS, mlz 286 (M-C0 2,55%), 268 (37), 253 (30),
14 242 (44),227 (59),210 (8),199 (17), 181 (12), 149
OH Me
(11), 128 (IS), liS (21),91 (100),77 (24),63 (27),
~
COOH 55 (52), 51 (35); positive FAB: mlz 331
16 (M+H+,26% )
Me 0 OH
TLC: RF A: 0.10, B: 0.14, C: 0.10, G: 0.28
COOMe StL: not yet found in lichens
15
Lit: Elix et al. 1992a
8-0-Methylpannaric acid
Crystals, mp 226-228C
(8-0-Methylpannarsaure)
UV: 259-264, S 280-285, S 305-315nm
IH-NMR (acetone-d6 ): 2.50 (3H,s,Me-16), 3.23 C17H;407 (330.28)
(3H,s,Me-14), 3.94 (3H,s,15-COOMe), 6.78 (1H,
s,H-7), 6.94 (1H,s,H-4)
**
14 Cream-coloured crystals (acetone-n-hexane),
OMe Me
mp 227-229C
COOH lH-NMR (acetone-d6 ): 2.80 (3H,s,Me-15), 3.03
16 (3H,s,Me-14), 6.71, 6.83 (2x1H,2xd,J=2.2Hz,H-
Me 0 OH
4 5,H-7), 6.87 (1H,s,H-4), 8.74, 11.37 (2x1H,2xs,
eOOH 2x-OH)
15
MS, m/z 272 (M+,30%), 255 (19), 254 (100), 229
(10),228 (62),227 (25), 199 (6), 198 (26)
Needles (acetone-n-hexane), mp 255-25rC
lH-NMR (acetone-d6 ): 2.75 (3H,s,Me-16), 3.26
Wedin
(3H,s,Me-14), 4.21 (3H,s,MeO-8), 7.05 (1H,s,
TLC: RF A: 0.23, B: 0.43, C: 0.25
H-7), 7.08 (1H,s,H-4), 8.29 (2H,s,2x-COOH)
HPLC: RJ 0.10
MS, mlz 286 (M-C0 2,100%), 271 (35),225 (11),
134 (30), 115 (11), 77 (11), 71 (15), 63 (10), 57
(21), 51 (13)
StL: Schizopelte californica Th.Fr. Pannaric acid (Pannarsaure)
Lit: Naidu 1993
'
CI6 H 12 0 7 (316.26)
**
Methyl porphyrilate 14
(Porphyrilsauremethylester) OH Me
eOOH
C17H 12 0 7 (328.27)
'6
Me 0 OH
OH 14 0 4
eOOH
M'4#.~ COOMe
Needles (acetone), mp 243-245C
React: NaOCI green, FeCl3 (EtOH) blue
UV (MeOH): 247 (4.52), 318nm (3.92)
IR (KBr): 744, 754, 810, 850, 1000, 1100, 1160,
Needles (pyridine: acetic acid = 1: 1), mp >
1252, 1390, 1444, 1590, 1642,3150, 3400cm-1
320C (dec.)
lH-NMR (l00MHz,DMSO-d6 ): 2.47 (3H,s,Me-
MS, mlz 328 (M+), 299, 270, 241
16), 2.85 (3H,s,Me-14), 6.65 (1H,s,H-4), 6.91
TLC: A: 23, B': 17, C: 11, E: 5, G: 38
(lH,s,H-7), 10.8 (2H,bs,2xHO-), 12.9 (2H,s,2x-
StL: Psoroma tenue Henssen
COOH)
Lit: Renner et al. 1981
MS, m/z 316 (M+,13%), 298 (43),272 (100),254
(79),228 (97), 198 (37), 114 (26)
Norascomatic acid (Norascomatsaure) Deriv: Diacetylpannaric acid, needles (MeOH-
H 20), mp 240C, by boiling pannaric acid with
ClsHl20S (272.25) Ac 20-pyridine for 5 min
StL: Leproloma membranaceum (Dicks.) Vain.
iJc(x
15 14
ME.' ME.' 9 TLC: A: 5, B: 28, B': 23, C: 10
eOOH HPLC: RJ 6
6 3
Lit: C.F. Culberson 1969; Elix 1972; Jakupovic
HO 0 OH and Huneck 1989
(-)-Placodiolic acid [(-)-Placodiolsaure] Needles (EtOH), mp 300-302C (dec.)

React: NaOCl green, FeC13 (EtOH) indigo blue
Cl9H200S (376.35)
UV (MeOH): 247 (4.45), S 260 (4.32), S 284
(4.09), 330nm (3.57)
~e IR (KBr): 670, 700, 740, 790, 855, 905, 990, 1032,
1070, 1102, 1162, 1230, 1280, 1320, 1338, 1390,
o 1440, 1475, 1500 1600, 1675, 1720, 3200,
3450cm-1
Me IH-NMR (400MHz,DMSO-d6): 2.50 (3H,s,Me-
15
16) 5.62 (2H,s,-CH 2-14), 6.65 (1H,s,H-7), 7.08
Weak yellowish plates (MeOH), mp 156-158C, (1H,s,H-4)
raW - 231 (CHC13 , c 0.875) MS, m/z 314 (M+), 298,270,241
React: KOH yellow, FeCl3 (EtOH) red-brown Deriv: Diacetylporphyrilic acid, needles (EtOH),
UV (MeOH): 230 (4.30),282 (4.45) 337nm (3.47) mp 262-265 c, by boiling porphyrilic acid with
IR (KBr): 680, 690, 770, 784, 838, 880, 902, 964, ACzO-pyridine for 5 min
990, 1005, 1020, 1080, 1138, 1200, 1284, 1370, StL: Haematomma ochroleucum (Necker)
1422, 1550, 1630, 3000,3250, 3550 cm- 1 Laundon
IH-NMR (60MHz,CDC13 ): 1.46 (3H,s,Me-13), TLC: A: 9, B: 11, B': 11, C: 5, E: 27
2.05 (3H,s,Me-16), 2.69 (3H,s,Me-15), 2.76 HPLC: RJ 7
(3H,s,Me-18), 3.23 (3H,s,C-5-0Me), 3.37 (2H, MC: Fig. 49A,B
q,J=18Hz,-CH 2-4), 10.36 (1H,s,HO-10), 14.38 Lit: C.F. Culberson 1969; Jakupovic and Huneck
(lH,s,HO-8) 1989
MS, m/z 376 (M+,1000/0), 361 (30), 345 (5), 344
(8),329 (8), 260 (25),250 (30), 235 (45),234 (30),
(-)-Pseudoplacodiolic acid
233 (48),217 (12)
[( -)-Pseudoplacodiolsaure]
Deriv: (-)-Diacetylplacodiolic acid, prisms
(MeOH), mp 184-185C, [an4 - 229 (CHC13, c Cl9HzoOs (376.35)
0.524), from (-)-placodiolic acid with Ac20-
H 2S0 4
StL: Rhizoplaca chrysoleuca (Sm.) Zopf
TLC: A: 65, B: 63, B': 60, C: 67, E: 21
HPLC: Rl27 o
MC: Figs. 48D, 59B,C
Lit: Huneck 1972c; Connolly et al. 1984a Me
15
Yellow prisms (MeOH), mp 180-182C, [am -

Porphyrilic acid (Porphyrilsaure)
218 (CHC13 , c 0.293)
C l6 H lO 0 7 (314.24) React: KOH yellow, FeC13 (EtOH) red-brown
UV (MeOH): 205 (3.95),230 (4.13), 284 (4.33), S
14
340nm (3.30)
IR (KBr): 680, 790, 812, 850, 882, 914, 968, 994,
1030, 1066, 1082, 1112, 1136, 1162, 1190, 1210,
Me 1290, 1310, 1358, 1380, 1422, 1444, 1468, 1490,
16
eOOH 1550, 1626,3000,3200, 3500cm-1
IH-NMR (60MHz,CDCI3): 1.48 (3H,s,Me-13), TLC: A: 42, B: 27, B': 22, C: 46

2.10 (3H,s,Me-16), 2.67 (3H,s,Me-CO-), 2.70 HPLC: Rl16
(3H,s,Me-CO-), 3.26 (3H,s,C-5-0Me), 3.45 MC: Fig. 49C
(2H,q,J=18Hz,-CH z-4), 10.20 (lH,s,HO-I0), Lit: Huneck et al. 1970b; C.F. Culberson et al.
13.16 (lH,s,HO-8), 17.88 (lH,s,HO-3) 1977b; Sargent and Stransky 1982; Jakupovic
MS, mlz 376 (M+,100%), 361, 345, 344, 329, 301, and Huneck 1989
292, 279,260, 250, 236, 235, 234, 233, 219, 217,
215,207, 191, 167, 149, 143, 123, 108, 94
(+)-Sodium usneate [(+)-Natriumusneat]
StL: Rhizoplaca chrysoleuca (Sm.) Zopf
TLC: A: 58, B: 52, B': 46, C: 57 E: 22 C1sH1SONa (366.29)
HPLC: Rj 25
MC: Fig. 66B,C,D
Lit: Huneck et al. 1981
NaO
Schizopeltic acid (Schizopeltsaure) Me
'
Cl9H1S07 (358.33)
**
14 Yellow needles (MeOH-HzO), mp > 240C
OMe Me (dec.), [ajb4 + 275.4 (acetone,c 0.62)
~OOMe UV (MeOH): 225 (4.47), 290nm (4.51)
16 IR (KBr): 700, 738, 768, 810, 834, 882, 940, 980,
Me 0 OMe 1004, 1038, 1068, 1116 1134, 1180, 1238, 1284,
4
eOOH 1320, 1450, 1470, 1516, 1620, 1690, 2700, 3000,
15 3500cm-1
StL: Lecanora stenotropa Nyl.
Needles (MeOH), mp 233-234C (dec.) Lit: Huneck 1982
UV (MeOH): 236 (4.62), 270 (4.29), 286 (4.26),
302 (4.07), 312nm (4.12)
Strepsilin
IR (KBr): 710, 740, 760, 800, 825, 870, 945, 980,
1000, 1030, 1058, 1090, 1105, 1120, 1160, 1190, ClsHIOOS (270.23)
1230, 1270, 1300, 1330, 1375, 1450, 1505, 1590,
1618, 1680, 1715,2700,2900,3000, 3500cm-1 15
lH-NMR (270MHz,DMSO-d6 ): 2.55 (3H,s,Me-
14), 2.68 (3H,s,Me-16), 3.82 (3H,s,C-3-0Me),
3.83 (3H,s,C-8-0Me), 3.97 (3H,s,-COOMe),
7Lho
6.87 (lH,s,H-7) 7.33 (IH,s,H-4) HoMoMoH
5 4
MS, mlz 358 (M+,100%), 343 (I5), 327 (40), 311
(20) Prisms or needles (acetic acid), mp 324C
Deriv: Dimethyl di-O-methylpannarate, needles React: NaOCI green, FeCl3 (EtOH) blue
(MeOH), mp 165-166C, from schizopeltic acid UV (MeOH): 242 (4.42),256 (4.23), S 274 (4.06),
with excessive CHzNz in EtzO-MeOH at room S 298 (4.01), 308 (4.10), S 330nm (3.65)
temperature for 12 h IR (KBr): 670, 685, 720, 770, 790, 838, 850, 992,
StL: Schizopelte californica Th.Fr. 1025, 1040, 1060, 1078, 1140, Ir64, 1185, 1225,
1270, 1335, 1410, 1425, 1448, 1470, 1518, 1588, Lit: C.F. Culberson et al. 1983; Elix and Kennedy
1618, 1700,2950,3330, 3500cm-1 1985
IH-NMR (270MHz,DMSO-d6 ): 2.63 (3H,s,Me-
15), 3.35 (2H,s,2xHO-), 5.82 (2H,s,-CH2-14),
(+)- and (-)-Usnic acid
6.62 (IH,d,H-7), 6.82 (IH,d,H-5), 7.04 (IH,s,
[(+)- und (-)-Usninsaure]
H-4)
2: 107.3, C-3 or C-I0: 155.4, 157.1, C-4: 98.2, C-
5: 95.6, C-6 or C-11: 157.5, 160.5, C-7: 113.6,
C-8: 131.9, C-9: 168.8, C-12: 113.4, C-13: 110.9, HO
C-14: 69.4, C-15: 20.4
StL: Di-O-methylstrepsilin, needles (benzene), Me
o
mp 250-251, from strepsilin with excessive ,6 Me a Me
CH2N2 in Et20-MeOH in 12h 13 15
StL: Cladonia strepsilis (Ach.) Grognot (+)-{12R)-Usnic acid
TLC: A: 39, B: 21, B': 26, C: 23, E: 7
HPLC: RJ 7
HO
MC: Fig. 49D
Lit: C.F. Culberson 1969; Brewer and Elix 1972;
Gollapudi et al. 1994
Me
(-)-(12S)-Usnic acid
Subdidymic acid (Subdidymsaure)
C2oH220S (342.38) Yellow prisms (CHCI3-EtOH or benzene), mp
203C, [aUf + 495 (CHCI3, c 1.00) respectively-
495
React: KOH yellow, KOH + NaOCI deep yellow
UV (EtOH): 220 (4.44), 290 (4.45), S 325 nm
(3.85)
IR (KBr): 704, 810, 825, 848, 938, 965, 998, 1030,
1042, 1070, 1118, 1142, 1190, 1220, 1290, 1320,
1338, 1360, 1380, 1425, 1460, 1550, 1630, 1686,
3000, 3550 cm-1
Crystals (CHCI3 -n-heptane), mp 158.5-160C IH-NMR (400MHz,CDCI3 ): 1.75 (3H,s,Me-13),
IH-NMR (CDCI3): 1.03 ,(6H,m,Me-3',Me-3"), 2.10 (3H,s,Me-16), 2.66 (3H,s,Me-15), 2.67
1.73 (4H,m,-CH 2-2',-CH2-2"), 3.07 (2H,m,- (3H,s,Me-18), 5.92 (IH,s,H-4), 11.02 (IH,s,C-
CH 2-1'), 3.58 (2H,m,-CH 2-1"), 3.93 (3H,s,- 10-0H), 13.31 (lH,s"C-8-0H), 18.84 (IH,s,C-
OMe), 6.85, 6.98 (2xlH,2xd,J=3Hz,H-5,H-7), 3-0H)
7.05 (IH,s,H-4) 13C-NMR (22.63MHz,CDCI3 ): C-l: 198.2, C-2:
MS, m/z 342 (M+,35%), 324 (100), 298 (26), 295 179.1\:, C-3: 155.1, C-4: 98.3, C-5: 101.7, C-6:
(13),280 (7),267 (7),240 (8) 99.8, C-7: 109.5, C-8: 157.6, C-9: 104.2, C-I0:
StL: Cladonia cristatella Tuck., Cladonia 164.1, C-ll: 105.4, C-12: 59.2, C-13: 27.4, C-14:
macilenta Hoffm. 200.1, C-15: 32.0, C-16: 7.7, C-17: 201.3, C-18:
30.9
3.12 Diphenylether 229
MS, mlz 344 (M+,60%), 260 (70),233 (100),217 Crystals (CHCI3), mp 138-139C
{20) React: N aOCI red, PeCl3 violet
Deriv: (+)-8,10-Diacetylusnic acid, pale yellow UV (MeOH): 212 (4.44), S 238, 245 (4.64), 290
needles (MeOH), mp 202C, [am + 200 (CHCI3,c (3.83), 314nm (3.89)
1.00), from (+)-usnic acid with Ac20-H2S0 4 at IR (KBr): 1662, 1683, 1688,3387 cm-1
room temperature in 5 h IH-NMR (90MHz,acetone-d6 ): 0.84, 0.91 (2x3H,
StL: (+)-Usnic acid: Evernia prunastri (1.) Ach., 2xt,J=6.2Hz,2x-Me), 1.20-1.70 (12H,m,6x-
(-)-usnic acid: Cladonia stellaris (Ach.) Pouzar CH 2- ), 1.89 (2H,m,-CH 2-3"), 2.49 (2H,t,J=
et Vezda 7.2Hz,-CH 2-3"'), 3.15 (2H,s,-CH 2-1"'), 6.18, 6.52
TLC: A: 70, B: 70, C: 71, E: 23, G: 88 (2xlH,2xdJ=2.0Hz,H-3,H-5), 6.31 (IH,s,H-l"),
HPLC: Rr 36 6.48 (1H,s,H-3')
MC: Pig. 50A,B MS, m/z 495 (9%), 494 (M-HzO, 34), 468 (10),
Lit: c.P. Culberson 1969; Norrestam et aL 1974; 450 (5), 371 (10), 370 (29), 369 (6), 352 (5),254
Behrens et al. 1976; Huneck et al. 1981; Ribar et (3),249 (4), 248 (4)
aL 1993 StL: Asahinea chrysantha (Tuck.), W.Culb. et
C.Culb., Parmelia birulae Elenk.
3.12 TLC: A: 0.70, B: 0.06, C: 0.07
Diphenylether Lit: Krivoshekova et al. 1983a; Stepanenko et al.
1985
~-Alectoronic acid (~-Alectoronsaure)
C2sH3209 (512.58)
7"
Me Me
HO o HO 3 o
Me
Buellolide (Buellolid) Canesolide (Canesolid)

Cl8 H 1S CIP6 (433.67) Cl8Hl4Cl406 (468.12)
8 a Cl 7'
Me
~
B
C l f t Me0 4'
Cl 0 M e a W Cl
Mea 4 3 a Cl
Me Mea a~aMe
7' Cl CI
Crystals (CH 2CI2-n-pentane), mp 170-173 DC
UV: 224 (4.64), 259 (4.19), S 288 (3.68), 295 Crystals (CH 2CI2-n-pentane), mp 158-160 DC
(3.71), 320nm (2.77) IR (CCI 4): 1788cm-1
IR (CCI4): 1781 cm- 1 IH-NMR (90MHz,CDCI3): 2.25 (3H,s,Me-7'),
IH-NMR (90MHz,CDCI3): 2.28 (3H,s,Me-7'), 3.59,3.89,4.01 (3x3H,3xs,3xMeO-), 5.16 (2H,s,
3.76, 3.85, 3.94 (3x3H,3xs,3xMeO-), 5.23 (2H,s, -CH2-8)
-CH2-8), 6.01 (1H,s,H-3) MS, m/z 472 (M+,130/0), 471 (12), 470 (50), 469
MS, m/z 436 (M+,120/0), 435 (8),434 (37), 433 (7), (22),468 (100), 467 (18),466 (72),455 (28),454
432 (34),223 (13),222 (8), 221 (69),220 (12),219 (12),453 (53),452 (10),451 (43),433 (13),431
(100), 178 (11), 176 (10), 169 (9) (13),221 (16),219 (10),205 (12), 178 (14), 176
StL: Diploicia canescens (Dicks.) Massal. (21)
TLC: A: 72, B': 45, C: 63, E: 51 StL: Diploicia canescens (Dicks.) Massal.
HPLC: RJ 23 TLC: A: 73, B': 63, C: 71, E: 45
Lit: Sala et al. 1981 Lit: Sala et al. 1981
~-Collatolic acid (~-Collatolsaure)

C29H3409 (526.56)
7"
Me Me
Mea o MeO
3
o
Me Me
7 111
Prisms (benzene), mp 165C (Asahina et aI. IH-NMR (I00MHz,acetone-d6): 0.86 (3H,t,Me-

1933), 117C (EtOH, Krivoshchekova et aI. 7"), 1.10-1.72 (IOH,m,-CH 2-2"-7"), 2.45 (3H,s,
1983a), 106-108C (Stepanenko et al. 1985) Me-8), 3.06 (2H,m,-CH 2-1"), 3.72 (3H,s,MeO-),
React: NaOCl red, FeCl3 violet 6.09, 6.69 (2H,2xd,J=2Hz,H-3,H-5), 6.41 (IH,
UV (EtOH): 248 (4.42), 276 (3.70), 290 (3.57), s,H-3')
320 nm (3.62) MS, m/z 432 (M+,6%), 414 (7), 396 (5), 389 (9),
IR (CHCl3): 1662, 1676, 1694cm-1 388 (37), 386 (7), 371 (27), 370 (100), 345 (14),
IH-NMR (90MHz, acetone-d6): 0.87 (6H,m,2x 344 (56), 342 (12), 328 (6), 326 (9), 288 (7), 286
Me-), 1.25-2.00 (14H,m,7x-CH 2-), 2.52 (2H,t,J= (9), 260 (12), 259 (19), 257 (12), 249 (13), 165
7.9Hz,-CH2-3"), 3.20 (2H,s,-CH 2-1/ff), 3.79 (3H, (30),44 (41)
s,MeO-4), 6.26, 6.66 (2xlH,2xd,J=2.3Hz,H-3, StL: Neophyllis melacarpa (Wils.) Wils.
H-5), 6.39 (IH,s,H-l"), 6.48 (IH,s,H-3') TLC: RF 0.47 (n-hexane: Et20: HCOOH = 13: 8:
MS, mlz 509 (4%), 508 (M-H 20,11), 483 (13), 2)
482 (41),464 (7), 386 (4), 385 (24),384 (100), 383 HPLC: Rr 37
(15),366 (3), 286 (3), 283 (5),262 (6) Lit: Chester and Elix 1980
Deriv: Methyl ~-collatolate, needles (MeOH),
mp 75C, from ~-collatolic acid with the calcu-
Epiphorellic acid I (Epiphorellsaure I)
lated amount of CH2N2 at Oc. C. Collatolone,
needles (EtOH), mp 142C, by boiling of ~ C26H340S (474.53)
collatolic acid with formic acid
StL: Asahinea chrysantha (Tuck.) W.Culb. et 5"
C.Culb., Asahinea scholanderi (Llano) W.Culb. Me
et C. Culb.
TLC: A: 0.82, B: 0.10, C: 0.26
Lit: Asahina et al. 1933; Krivoshchekova et al.
1983a; Stepanenko et al. 1985
Congrayanic acid (Congrayansaure)

C23H2S0S (432.45)
8 Me
Me 5'"
5~COOH HO
Me oN---
3
0 -~~'- Crystals (acetone-n-heptane), mp 158-160C
IR (KBr): 1150, 1250, 1280, 1370, 1430, 1610,
1625, 1700, 1710, 2860-2960, 3420cm-1
IH-NMR (CDCl3): 0.90 (6H,m,Me-5",Me-5/ff),
1.37 (12H,m,-CH z-2"-4",2/ff-4/ff), 2.57 (2H,t,J=
7Hz,-CH z-l"), 2.90 (2H,t,J=7Hz,-CH z-l/ff), 3.70
(3H,s,C-4' -OMe), 3.90 (3H,s,-COOMe), 5.83
Me (1H,d,J=2.5Hz,H-3), 6.40 (1H,d,J=2.5Hz,H-5),
7" 6.50 (1H,s,H-3')
Prisms (Et20-n-pentane), mp 183-183.5C 13C-NMR (acetone-d6): C-l: 115.1, C-2: 163.8,
React: NaOCl red C-3: 99.3, C-4: 158.5, C-5: 109.6, C-6: 143.7, C-
7: 168.7, C-1": 30.3, C-2": 29.6, C-3": 32.0, C-4": 2.5Hz,H-3), 6.36 (lH,d,J=2.5Hz,H-5), 6.25 (lH,
22.7, C-5": 14.0, C-1': 104.5, C-2': 159.4, C-3': s,H-3'), 9.70 (2H,m,2xHO-)
98.5, C-4': 157.8, C-5': 140.6, C-6': 134.4, C-7': 13C-NMR (acetone-d6): C-1: 115.2, C-2: 163.9,
173.6, C-1"': 31.3, C-2"': 28.8, C-3"': 32.5, C-4"': C-3: 99.5, C-4: 158.5, C-5: 109.8, C-6: 142.8, C-
22.7, C-5"': 14.0, -COOMe: 51.7, C-4'-OMe: 56.0 7: 168.5, C-l": 28.3, C-2": 43.9, C-3": 209.5, C-
MS, m/z 474 (M+,15%), 456 (20), 430 (100), 399 4": 35.9, C-5": 8.0, C-1': 104.7, C-2': 159.7, C-3':
(25),355 (5),285 (5),271 (6), 193 (10), 192 (9), 98.9, C-4': 158.0, C-5': 140.6, C-6': 134.4, C-7':
137 (5) 173.4, C-l"': 31.2, C-2"': 28.7, C-3"': 32.8, C-4"':
Deriv: Methyl epiphorellate I, mp 135-137C 23.0, C-5"': 14.3, -COOMe: 52.0, C-4' -OMe: 56.3
(acetone-n-pentane), from epiphorellic acid I MS, m/z 444 (M-CO z,72%), 413 (13), 381 (33),
with CHzNz 355 (100), 337 (20) 285 (96), 271 (17), 193 (50),
StL: Coelopogon epiphorella (Nyl.) Brusse et 192 (54), 163 (22), 138 (21), 137 (67), 57 (58)
Karnef. Deriv: Methyl epiphorellate II, mp 108-109 c
TLC: A: 44, B': 46, C: 35 (CHCI3-n-hepatane), by reaction of epiphorellic
HPLC: Rj 24 acid II with CH 2Nz
Lit: Fiedler et al. 1986; Elix and Jenie 1989 StL: Coelopogon epiphorella (Nyl.) Brusse et
Karnef.
TLC: A: 35, B': 26, C: 23
Epiphorellic acid II (Epiphorellsaure II)
HPLC: Rj 13
CZ6H3Z09 (488.51) Lit: Fiedler et al. 1986; Comber et al. 1989
5"
Me 2'"-0- Ethyl-~-alectoronic acid (2'" -0- Ethyl-~
alectoronsaure)
C30H3609 (540.59)
MeO 3'
HO
Me
5/11
Crystals (acetone-n-heptane), mp 146-148, o

150-152C
IR (KBr): 740, 830, 1l00, 1150, 1215, 1240, 1280,
1370, 1415, 1440, 1450, 1485, 1610, 1625, 1655,
1700, 1740,2860,2960, 3360cm-1
IH-NMR (acetone-d6): 0.82 (3H,t,J=7Hz;Me-
5"'), 1.00 (3H,t,J=7Hz,Me-5"), 1.32 (4H,m,H-
4"',H-3"'), 1.48 (2H,m,H-2"'), 2.45 (2H,q,J=7Hz,
H-4"'), 2.79 (4H,m,H-l",H-2"), 3.80 (3H,s,C- Crystals (EtzO-n-hexane), mp 182C
4' -OMe), 3.86 (3H,s,-COOMe), 5.78 (lH,d,J= React: N aOCI red
UV (MeOH): 215 (4.27),245 (4.76), S 259 (4.37), Needles (EtOH-H 20), mp 250-251 C
S 269 (4.29),290 (3.87), 318nm (4.10) React: FeCl3 (CHCI3-pyridine) green, NaOCI red
IR (KBr): 930,1035,1070, 1l05, 1160, 1256, 1355, IR (Nujol): 1680, 1726, 3280 cm-1
1460, 1480,1595, 1658, 1675, 1690, 3280cm-1 StL: Xanthoparmelia amplexula (Stirt.) Elix et
lH-NMR (500MHz,CDCI3): 0.84 (3H,t,J=5.9Hz,- Johnston
Me), 0.89 (3H,t,J=6.9Hz,-Me), 1.07 (3H,t,J= TLC: RF A: 0.31, B: 0.14, C: 0.05
6.9Hz, Me-CH 2-O-), 1.20 (2H,m,-CH 2-), 1.24- Lit: Gream and Riggs 1960; Elix et al. 1985c
1.64 (l2H,m,6x-CH 2-), 1.33 (2H,m-CH 2-), 1.63
(2H,m,-CH z-), 1.90 (2H,m,-CH z-3"'), 2.44 (2H,
Leprolomin
t,J=7.5Hz,-CH z-3") , 2.90, 3.10 (2x1H,2xbd,J=
15.8Hz,-CHz-1"'), 3.57, 3.63 (2H,m,Me-CH z- CZOH 22 0 S (390.38)
0-), 6.13 (lH,s,H-1"), 6.32 (lH,bs,H-5), 6.40
(1H,s,H-3') 6.46 (1H,d,J=1.5Hz,H-3), 8.98, 11.0 8
(2X1H,2xbs,2x-OH) 9 OH ME'
13C-NMR (125.7MHz,CDCI 3): C-1: 102.5, C-2: ME'~r
161.8, C-3: 103.4, C-4: 162.8, C-5: 105.6, C-6:
142.2, C-7: 160.8 C-1': 99.9, C-2': 163.8, C-3': ME'O ~
4 3 0
103.4, C-4': 156.9, C-5': 133.3, C-6': 131.7, C-7':
169.1, C-1": 103.2, C-2": 159.1, C-3": 31.6, C-4":
23.1, C-5": 31.1, C-6": 22.3, C-7": 13.9, C-1"': Pale yellow prisms (cyclohexane-EtOAc), mp
35.5, C-2"': 107.7, C-3"': 33.1, C-4"': 26.4, C-5"': 238-239C
31.2, C-6"': 22.4, C-7"': 13.9, Me-CHz-O-: 15.2, UV (EtOH): 224 (4.41), 288 (4.46), 338nm (3.95)
Me-.GHz-O-: 58.1 lH-NMR (100MHz,CDCI3-DMSO-d6): 2.00, 2.20,
MS, m/z 494 (M-EtOH,2%), 476 (1), 279 (10), 2.72, 2.83 (4x3H,4xs,4xMe-), 3.66, 3.81 (2x3H,
167 (31), 150 (12), 149 (100); FABS: 541 (M+H) 2xs,2x-OMe), 5.77 (lH,s,H-3), 9.49,13.59,13.91
StL: Alectoria sarmentosa Ach.; very probably (3x1H, 3xs, 3xHO-)
an artefact by reaction of alectoronic acid with 13C-NMR (67.89MHz,CDCI3 :CD30D = 1:1): C-
ethanol during extraction 1: 106.27, C-2: 162.07 C-3: 87.68, C-4: 161.07,
Lit: Gollapudi et al. 1994 C-5: 109.88, C-6: 158.64, C-7: 202.12", C-8:
31.07b , C-9: 7.26e , C-1': 108.13, C-2': 157.16, C-
3': 105.21, C-4': 154.62, C-5': 124.31, C-6':
Iso-norlobaridone (Iso-norlobaridon)
153.63, C-7': 202.63", C-8': 32.90b, C-9': 8.85 e .
C23H2606 (398.44) (values marked. with a, band c may be
ME' exchanged)
MS, m/z 390 (M+,100%), 348 (87),332 (10),330
(9),329 (7),315 (9),197 (17), 195 (37),194 (46),
181 (60), 179 (47), 165 (10), 155 (8), 154 (10)
OH Deriv: Triacetylleprolomin, prisms (cyclohex-
ane), mp 121.5-122.5C, from leprolomin with
AC zO-H zS0 4 at 40C in 30min
StL: Psoroma leprolomum (Nyl.) Riis.
TLC: A; 63, B: 55, B': 54, E: 35
HPLC: Rj 19
ME' Lit: Elix et al. 1978a
Loxodinol Needles (CHClz-cyclohexane), mp 134-136C

IH-NMR (acetone-d6): 0.88 (6H,bt,Me-7",Me-
C2sH3009 (474.49)
7"'), 1.33 (lOH,m,-CH 2-2"-6",2"'-6"'), 2.77, 3.07
II (2x2H,2xbt,-CH 2-1",1"'), 3.81 (6H,s,MeO-4,
5 MeO-3'), 6.15 (lH,s,H-5'), 6.49, 6.78 (2H,2xd,
Me
J=2.4Hz,H-3,H-5), 8.78 (2H,bs,-COOH,-OH)
MS, m/z 530 (M+,l %),486 (32),480 (13),456 (9),
452 (13),442 (7),424 (8), 249 (28),248 (100),218
HO OH (12), 206 (29), 203 (33), 190 (16), 175 (12), 133
7' (26), 121 (22)
HO
3
o COOMe StL: Micarea prasina Fr.
2'-0-Methylphysodone
Me
Sill (2' -0-Methylphysodon)
C26H3206 (440.52)
Needles (acetone-H20), mp 235-237C
React: NaOCl red 7"
UV (EtOH): 258, 295, 306nm Me
IR (KBr): 1700, 1735, 3440cm-1
IH-NMR (acetone-d6): 0.89 (6H,m,Me-5",Me-
5"'), 1.28 (lOH,m,-CH 2-3"-4",2'" -4"'), 2.86 (4H,
m-CH2-2",1"'), 3.95 (lH,s,7' -COOMe), 6.05,
6.62 (2x1H,2xs,H-3,H-5), 6.48 (1H,s,H-3') HO
MS, mlz 474 (M+,2%), 456 (20), 430 (35), 424
(20),398 (100),341 (20),221 (30) HO
3
o
StL: Xanthoparmelia scabrosa (Tayl.) Hale
Lit: Foo and Galloway 1979
Me
Methoxymicareic acid (Methoxymicaresaure) 5'"
C30H 42 0 S (530.64) Crystals, mp 198C

IR: 1685,3280, 3500cm-1
7" IH-NMR (200MHz,acetone-d6): 0.79, 0.94 (2x
Me
3H,2xt,Me-7",Me-5"'), 1.20 (4H,m,2x-CH 2-),
1.39 (4H,m,2x-CH 2-), 1.73 (4H,m,2x-CH 2-),
2.41, 2.51 (2x2H,2xt,-CH 2-3',-CH z-1"'), 3.78
(3H,s,MeO-2'), 6.06, 6.40 (2H,2xd,J=3Hz,H-
3,H-5), 6.26 (lH,s,H-1"), 6.37, 6.45 (2H,2xd,
J=2Hz,H-1',H-3')
13C-NMR (50.29MHz,acetone-d6): 14.2, 23.2,
5' 23.4, 27.6, 30.7, 31.5, 32.3, 32.8, 34.0, 56.0
(MeO-), 104.4, (C-3'), 101.9 (C-3), 102.3 (C-5),

105.0, 107.7 (C-1'), l35.2 (C-6'), l38.4 (C-5'),
143.7 (C-6), 151.6 (C-2'), 164.2 (C-4'), 159.3
(C-7), 159.7, 162.4, 166.0
MS, m/z 442 (10%),441 (47),440 (M+, 100),425
OH
(5),384 (14), 369 (5), 249 (10),248 (8),232 (12),
193 (8), 192 (22), 177 (8), 176 (17), 164 (6), 163 HO o
3
(10),150 (14),147 (8), l38 (9), l37 (15), l36 (8),
l35 (6), 134 (34), 105 (11), 91 (6),69 (8), 57 (9),
55 (9),43 (17),41 (18)
StL: Pseudevernia furfuracea (1.) Zopf Me
Lit: Gunzinger 1985 5'"
Micareic acid (Micaresaure) Needles (EtOH-H10), mp 192-193C, [a] + 12

React: FeCl3 (CHCI 3-pyridine) blue-green,
C19H4007 (500.61)
NaOCI red
7" UV (EtOH): 259 (4.15), 284 (3.86), S290nm
7'"
Me Me (3.82)
IR (Nujol): 1723, 3280cm-1
IH-NMR (60MHz,acetone-d6 ): 0.90 (6H,m,Me-
5",Me-5"'), 1.30 (10H,m,-CH z-3"-5",2"'-4"'),
2.10 (4H,m,-CH l -2",1"'), 6.07 (lH,d,J=1.8Hz),
6.32 (lH,d,J=2.6Hz), 6.42 (lH,d,J=2.6Hz), 6.60
(1H,d,J=1.8Hz) (H-3,5,1',3')
MS, m/z 416 (M+), 398, 372, 330, 315
Deriv: Dimethyllobariol, mp l39 C (benzene-n-
Needles (CH1Cl1-cyclohexane), mp 100-102C hexane), by methylation of norlobariol with
IH-NMR (acetone-d6 ): 0.87 (6H,bt,Me-7",Me- dimethyl sulphate-NaOH
7"'), 1.29 (10H,m,-CH l -2" -6",2'" -6"'), 2.65-3.05 StL: Xanthoparmelia scabrosa (Tayl.) Hale
(4H,m,-CH 1-1", 1"'), 3.81 (3H,s,MeO-4), 6.23, TLC: RF 0.11 (benzene:dioxane:AcOH = 180:
6.39 (2H,2xd,J=2.5Hz,H-3,H-5), 6.52, 6.76 (2H, 45:5); A:12, B':18, C:l, E:5
2xd,J=2.5Hz,H-3',H-5'), 8.40 (2H,bs,-COOH, HPLC: Rj 11
-OH) Lit: Gream and Riggs 1960; Foo and Gwyn 1978;
MS, m/z 500 (M+,0.2%), 482 (11),456 (93),412 Elix and Ernst-Russell 1993
(36),372 (100), 366 (39), 353 (64),328 (43),249
(64), 165 (79), 150 (31), 124 (43)
N orlobariolmethylpseudoester
StL: Micarea prasina Fr.
Lit: Elix et al. 1984b C14H3007 (430.48)
Norlobariol
C13 H 28 0 7 (416.45)
TLC: A: 67, B': 41, C: 60, E: 34

HPLC: RJ 18
Lit: Elix et aI. 1984a
3.14
Diphenylmethanes
a
Bis-(2,4-dihydroxy-6-n-propylphenyl)-
methane [Bis-(2,4-dihydroxy-6-n-
propylphenyl)-methan 1
Cl9H2404 (316.38)
Needles (MeOH-H 20), mp lIS-120C
React: FeCl3 (CHCI3-pyridine) green, NaOCI red 3"1
3"
IR (Nujol): 1720, 3280cm-1 Me Me
StL: Xanthoparmelia amplexula (Stirt.) Elix et
Johnston
TLC: RF A: 0.28, B: 0.23, C: 0.03
Lit: Gream and Riggs 1960; Elix et al. 1985c
HO OH
3.13
Biphenyls React: NaOCI red
IH-NMR (CDCI3 ): 3.89 (2H,s,-CH 2-7), 6.18, 6.24
Contortin (2x2H,2xbs,H-3,H-5,H-3',H-5')
13C-NMR (CDC1 3 ): C-7: 21.8, C-l", C-l"': 35.9,
C-2", C-2"': 35.9, C-3", C-3"': 14.1
8 StL: Protousnea sp.
Me Lit: Kinoshita et al. 1994a
Mea
3.15
Me Nostoclides
9
Needles (cyclohexane), mp 129-130C N ostoclide I (Nostoclid I)

UV (EtOH): 229 (4.35), 277 (4.31), 345nm (3.98) C21HlsC1203 (389.26)
IR (Nujol): 1610cm-1
IH-NMR (CDCI3): 2.20 (6H,s,Me-9,Me-9'), 2.74
(6H,s,Me-8,Me-8'), 3.53, 3.82 (2x3H,2xs,MeO-
6,MeO-6'), 13.40 (2H,s,HO-2,2')
13C-NMR (CDCI 3): 9.6 (Me-9,9'), 31.6 (Me-8,8'),
111.7, 112.1, 115.7 (arom.C), 161.2, 161.4, 164.2
(arom.C-O-), 204.4 (C-7,7')
MS, m/z 418 (M+,1000/0), 403 (33), 400 (8), 388
(22),387 (84), 327 (14), 369 (30),43 (40)
StL: Psoroma contortum Mull.Arg.
3.16 Depsides 237
Prisms (MeOH), mp 186-187C StL: Nostoc phycobiont from Peltigera can ina
UV (MeOH): 250 (4.16), 350nm (4.51); MeOH + (1.) Willd.
NaOH: 262.5 (4.00), 400nm (4.26) Lit: Yang et al. 1993
lH-NMR (CDC13): 3.80 (2H,s,-CH 2-5), 7.21-7.32
(5H,m,H-7-H-11), 3.14 (1H,septet,J=7.2Hz,H- 3.16
12), 1.30 (6H,d,J=7.2Hz, Me-13,Me-14), 6.02 Oepsides
(lH,s,H-15), 7.73 (2H,s,H-17,H-21)
13C-NMR (CDC13): C-l: 170.4, C-2: 148.1, C-3: 3.16.1
138.7, C-4: 148.5, C-5: 30.2, C-6: 130.4, C-7-C- Didepsides
11: 127.0-129.1, C-12: 27.0, C-13, C-14: 21.8, C-
IS: 107.6, C-16: 126.4, C-17: 130.4, C-18: 122, Anziaic acid (Anziasaure)
C-19: 158.1, C-20: 122, C-21: 130.4
StL: Nostoc phycobiont from Peltigera canina
(1.) Willd.
Lit: Yang et al. 1993
Nostoclide II (Nostoclid II)

C21Hl9Cl03 (354.81)
Me
HO
Me
5/11
CI
OH
Needles (MeOH-H 20), mp 124C (dec.), flat
plates (CHC1 3-n-pentane), mp 139-140C
Yellow prisms (MeOH), mp 132-133C React: N aOCl red, FeC13 brownish violet
UV (MeOH): 241 (4.08), 355nm (4.45); MeOH + IR (KBr): 735, 785, 830, 900, 1020, 1070, 1140,'
NaOH: 259 (4.15), 418.5nm (4.50) 1160, 1185, 1200, 1240, 1310, 1350, 1415, 1450,
lH-NMR (CDC1 3): 3.79 (2H,s,-CH 2-5), 7.18-7.32 1470, 1500, 1610, 1640, 1660, 2900, 3000, 3200,
(5H,m,H-7-H-11), 3.14 (lI;I,septet,J=7.1Hz,H- 3550cm-1
12), 1.31 (6H,d,J=7.1Hz,Me-13,Me-14), 6.09 lH-NMR (60MHz,CDC13 ): 0.87 (6H,t,J=5Hz,Me-
(1H,s,H-15), 7.83 (1H,d,J=2.1Hz,H-17), 7.03 5",Me-5"'), 1.42 (12H,m,-CH 2-2"-4",-CH2-2"'-
(IH,d,J=8.5Hz,H-20), 7.61 (lH,dd,J=8.5Hz,H- 4"'), 2.96 (4H,t,J=7.5Hz,-CH 2-1",-CH 2-1"'), 6.32
21) (4H,2xq,J=2Hz,H-3,H-5,H-3',H-5'), 10.41 (4H,
13C-NMR (CDC1 3): C-l: 170.7, C-2: 147.3, C-3: bs,3xHO-,-COOH)
138.8, C-4: 152.2, C-5: 30.1, C-6: 131.3, C-7-C- MS, mlz 224 (60%), 206 (100), 191 (8), 180 (10),
11: 127.0-129.1, C-12: 27.0, C-13, C-14: 21.8, C- 178 (48), 177 (16), 168 (61), 164 (13), 163 (25),
IS: 108.9, C-16: 127, C-17: 131.3, C-18: 121, 151 (11), 150 (90), 124 (25), 123 (13), 122
C-19: 158.3, C-20: 117, C-21: 125.7 (29),121 (20),94 (10), 69 (11)
*
Deriv: Methyl anziate, mp 102C (MeOH-H 20), 9 8'
from anziaic acid with CH2N 2 in Et 20 at OC in
30s
Me, to-o 3~e2' OH
5 "
StL: Anzia japonica (Tuck.) Mull.Arg. 2 ~ " 7'
TLC: A: 40, B: 59, B': 55, C: 33 HO 4 3 OH ~ COOMe
HPLC: RI 35 CHO Me
MC: Fig. 17C 8 9'
Lit: C. F. Culberson 1969; Elix 1974 Prisms (CHCl3-MeOH), mp196C (dec.)
React: KOH yellow, PD yellow, FeCl3 red-brown
Arthoniaic acid (Arthoniasaure) UV (MeOH): 210 (4.20), 252 (4.16), 312nm
(3.57)
C29H3609 (528.58) IR (KBr): 790, 810, 830, 870,960,990,1010,1030,
1078, 1108, 1166, 1198, 1210, 1250, 1270, 1285,
Me
1360, 1382, 1410, 1458, 1580, 1652, 3000,
3500cm-1
IH-NMR (400MHz,CDCIJ: 2.09 (3H,s,Me-8'),
2.69 (6H,s,Me-9,Me-9'), 3.99 (3H,s,7'-
CO-O OMe COOMe), 6.40 (1H,s,H-5), 6.51 (1H,s,H-5'),
OH HO 10.36 (1H,s,CHO-8), 11.96 (1H,s,HO-2'), 12.51
(IH,s,HO-2), 12.56 (1H,s,HO-4)
13C-NMR (25.05MHz,CDCl3): C-l: 103.0, C-2:
169.0, C-3: 108.7, C-4: 167.5, C-5: 112.8, C-
6: 152.3, C-7: 169.6, C-8: 193.6, C-9: 24.4, C-l':
Me Me 116.8, C-2': 162.8, C-3': 110.4, C-4': 152.1, C-5':
116.0, C-6': 139.8, C-7': 172.1, C-8': 23.8, C-
Needles (EtOAc), mp 167-169C (dec.)
9': 9.4, C-7' -COOMe: 52.2
React: NaOCl orange-red, FeCl3 (EtOH) red-
MS, m/z 375 (9%), 374 (M+,30), 197 (30), 196
brown, heating with KOH and CHCl3blue-violet
(100), 180 (35), 179 (98), 178 (26), 177 (25), 176
UV (MeOH): 270 (4.28), 300nm (4.15)
(35), 165 (61), 164 (94), 163 (13), 151 (14), 150
MS, m/z 262, 248, 206
(61), 149 (26), 137 (17), 136 (78), 135 (22), 85
Deriv: Methyl arthoniate, needles (MeOH), mp
(15),83 (30),79 (12), 77 (22), 69 (15), 67 (24),,66
159-160C, from arthoniaic acid with CH 2 N2 at
(11),65 (12),55 (17),52 (13), 51 (17),43 (22),41
OC in 1 min
(15)
IR (KBr): 835,1060,1095,1148,1200,1270,1445,
Deriv: Pentaacetylatranorin, prisms (MeOH),
1595,1630,1670, 1697, 1~12, 1724, 3345cm-1
mp 153-154C, from atranorin with Ac2 0-
StL: Arthonia impolita (Ehrh.) Borr.
H 2S0 4
TLC:A:31,B: 15,C: 13
StL: Parmotrema tinctorum (Nyl.) Hale
HPLC: Rl 18
TLC: A: 75, B: 78, B': 73, C: 79, E: 57, F: 85
Lit: Huneck et al. 1970a
HPLC: RI 38, RI (SA) 100
MC: .figs. 17D; 18A,B,C,D
Atranorin Lit: C. F. Culberson 1969; Brassy et al. 1982
3.16 Depsides 239
Baeomycesic acid (Baeomycessaure) Barbatic acid (Barbatinsaure)

Cl9HISOS (374.33) Cl9H2007 (360.35)
* #'
9 8'
Me 7 ~e 9 8'
Me 7 Me
6 , CO-O 3 2' OH
5 ,
C O4'- o *'OH
'
2 4 " 7' 5
2 ' 7'
Me 0 4 3 OH 5' 6' COOl-!
MeO 4 3 OH 5' 6' COOH
CHO Me
8 9' Me Me
8 9'
Prisms (acetone-H20), mp 224-225C (dec.)
React: PD yellow, FeCl3 purple Needles (benzene), mp 187 D C (dec.)
UV (MeOH): 212 (4.41), 247 (4.08), 288nm React: KOH + NaOCl orange, FeCl3 violet-blue
(3.84) UV (MeOH): 218 (4.57), 276 (4.27), 310nm
IR (KBr): 690, 740, 760, 790, 824, 900, 970, 1010, (3.86)
1058, 1082, 1135, 1170, 1200, 1220, 1250, 1350, IR (KBr): 735, 770, 820, 844, 855, 900, 930, 990,
1405, 1450, 1500, 1570, 1620, 1640, 1685, 1730, 1090, 1140, 1180, 1228, 1260, 1320, 1400, 1464,
2600, 3000, 3500 cm-l 1495, 1570, 1630, 1730,2600,3000, 3500cm-1
IH-NMR (60MHz;DMSO-d6-acetone-d6 ): 2.10, IH-NMR (270MHz,DMSO-d6 ): 1.98 (3H,s,Me-
2.50, 2.57 (3x3H,3xs,3xMe-), 6.49, 6.54 (2x1H, 8'), 1.99 (3H,s,Me-8), 2.46 (3H,s,Me-9'), 2.55
2xs,H-5,H-5'), 10.20 (1H,s,-CHO-8), 11.30 (3H,s,Me-9), 3.85 (3H,s,MeO-4), 6.58 (lH,s,H-
(1H,s,-OH), 12.56 (lH,s,-COOH) 5),6.68 (1H,s,H-5'), 10.73 (lH,s,HO-2)
!3C-NMR (25.05MHz,DMSO-d6 ): C-1: 112.2, C- !3C-NMR (acetone-d6 ): C-1: 111.1, C-2: 154.2,
2: 160.8, C-3: 108.2, C-4: 162.9, C-5: 104.3, C-6: C-3: 105.8, C-4: 164.7, C-5: 108.1, C-6: 141.7,
148.4, C-7: 165.3, C-8: 196.9, C-9: 20.9, C-1': C-7: 171.4, C-8: 8.5, C-9: 24.3, C-4-0Me:
115.9, C-2': 161.5, C-3': 113.2, C-4': 152.2, C- 56.7, C-l': 163.8, C-2': 111.9, C-3': 164.0, C-4':
5': 115.7, C-6': 139.0, C-7': 172.7, C-8': 8.9, C-9': 117.8, C-5': 142.4, C-6': 117.8, C-7': 174.8, C-
22.7, C-4-0Me: 56.3 8': 9.9, C-9': 25.4
MS, m/z 374 (M+,5%), 210 (0.8), 194 (12), 193 MS, m/z 360 (M+,l %),340 (1),316 (1), 196 (12),
(100),191 (9), 182 (1), 164 (3),136 (3),135 (3),79 182 (33), 180 (12), 179 (100), 178 (53), 177 (7),
(3), 77 (5),67 (3) 165 (11), 164 (62), 163 (9), 152 (12), 151 (6),150
Deriv: Methyl baeomycesate, prisms (acetone), (37), 149 (12), 148 (7), 138 (26), 137 (23), 136
mp 207 DC, from baeomycesic acid with CH2N 2 (74),135 (22), 123 (12), 122 (5), 121 (12),120 (7),
StL: Dibaeis baeomyces (L.fil.) Rambold et 119 (5),109 (7), 108 (15), 107 (35), 92 (5), 91 (21),
Hertel 83 (7), 81 (5), 80 (8), 79 (29), 78 (8), 77 (28), 67
TLC: A: 39, B: 40, B': 41, C: 42 (12), 65 (11), 63 (7), 55 (10), 53 (15), 52 (9), 51
HPLC: Rr 28 (13),50 (6),44 (14),43 (8),41 (6)
MC: Fig. 19B,C Deriv: Methyl barbatate, needles (MeOH), mp
Lit: C.F. Culberson 1969; Sundholm and Huneck 173 DC, from barbatic acid with CH1N z
1981 StL: Usnea barbata (L.) Wigg.
TLC: A: 44, B: 69, B': 67, C: 52
HPLC: Rr 37
MC: Pigs. 19D, 20A,B 10 8'

Lit: c.P. Culberson 1969; Elix and Norfolk 1975b
9 * M e7 ,Me
Me 1 CO-O 4 OMe
5 2 5'
Boninic acid (Boninsaure) MeO 4 3 OMe Me
9'
CZSH3Z0S (460.51) Me
8
3'/
~
MelV Prisms (CHCI3 ), mp 102-104C
OH IR (KBr): 850, 1280, 1450, 1620, 1730, 2900cm- 1
5 CO-O IH-NMR (60MHz,CDCIJ: 2.19 (9H,s,Me-9,Me-
4' 10,Me-l0'), 2.27 (3H,s,Me-9'), 2.30 (3H,s,Me-
MeO 3 OMe MeO 8), 2.36 (3H,s,Me-8'), 3.70 (3H,s,MeO-2'), 3.81
(6H,s,MeO-2,MeO-4), 6.63 (IH,s,H-l')
5'" 13C-NMR (25.15MHz,CDCI3 ): C-l: 120.9, C-2:
Me
158.9, C-3: 116.7, C-4: 154.6, C-5: 124.7, C-6:
Plates (benzene-n-pentane), mp 134.5C 135.2, C-7: 167.1, C-8: 9.7, C-9: 12.5, C-I0: 17.2,
React: PeCl3 purple C-2-0Me: 61.9, C-4-0Me: 60.1, C-l': 110.2, C-
IH-NMR (60MHz,CDCI3 ): 0.99-1.09 (6H,m,Me- 2': 155.8, C-3': 122.2, C-4': 148.6, C-5': 126.4, C-
3",Me-5"'), 1.27-1.86 (8H,m,-CH z-2",-CH z-2'" 6': 133.5, C-8': 9.7, C-9': 12.6, C-I0': 20.5,
-4"'), 2.78-3.05 (4H,m,-CH z-l",I"'), 3.85, 3.91, C-2' -OMe: 55.7
3.95 (3x3H,3xs,3xMeO-), 6.45 (2H,s,H-3,H-5), MS, m/z 372 (M+,4%), 207 (100), 193 (1), 166 (2),
6.48 (IH,s,H-5'), 10.35 (1H,bs,-COOH), 11.43 165 (2), 164 (6), 149 (3)
(1 H,bs,H 0-2') StL: Lecania brialmontii (Vain.) Zahlbr.
MS, mlz 416 (0.4%), 237 (5), 236 (30), 225 (5), TLC: RF A: 0.72, B: 0.75, C: 0.70
224 (35), 209 (5),208 (17),207 (100), 206 (5),205 Lit: Vinet et al. 1990a; Elix et al. 1993a
(5), 196 (10), 192 (6), 191 (34), 180 (7), 179 (9),
177 (7), 165 (5), 153 (6), 152 (14), 151 (12), 137 Brialmontin 2
(6),135 (7), 134 (10),121 (6), 120 (7),109 (5), 91
(8),78 (5),77 (9), 65 (6), 51 (5),44 (11),41 (6)
Deriv: Methyl boninate, plates (EtOH), mp
86C, from boninic acid with CHzN z 10 8'
StL: Ramalina boninensis Asah. 9 Me Me
TLC: A: 44, B: 34, B': 41, C: 46
HPLC: R, 31
Me#,
5 2
to-o 5' 4' "OMe
MC: Pigs. 20D MeO 4 3 OH Me

9'
Lit: c.P. Culberson 1969; Elix and Norfolk 1975a Me
8
Brialmontin 1
Pris~ns (CHCI 3 ), mp 106-109C
IR (KBr): 810, 1275, 1630, 1650,2495, 3400cm-1
IH-NMR (60MHz,CDCI3 ): 2.05 (6H,s,Me-
10,Me-l0'), 2.22 (3H,s,Me-9), 2.25 (3H,s,Me-
8'), 2.32 (3H,s,Me-8), 2.67 (3H,s,Me-9'), 3.75
3.16 Depsides 241
(3H,s,MeO-2'), 3.84 (3H,s,MeO-4'), 6.66 (IH, MS, mlz 412 (M+,0.2%), 410 (1), 232 (0.1),
s;H-1'), 11.42 (lH,s,HO-2) 230 (0.4), 215 (2), 213 (7), 197 (7), 196 (59),
13C-NMR (25.15MHz,CDCI3 ): C-1: 122.0, C-2: 186 (5), 184 (10), 164 (IOO), 163 (5), 137 (6),
161.9, C-3: 116.6, C-4: 156.9, C-5: 120.1, C-6: 136 (62), 135 (7), 108 (5), 107 (7), 79 (6), 77
138.0, C-7: 170.4, C-8: 9.6, C-9: 12.6, C-10: 19.3, (7), 67 (5), 65 (5), 55 (5), 53 (6), 51 (6), 44
C-4-0Me: 60.0, C-1': 110.2, C-2': 156.8, C-3': (8)
120.0, C-4': 150.2, C-5': 125.0, C-6': 135.2, C-7': Deriv: Chloroatranol, orange-yellow crystals
20.4, C-8': 9.1, C-9': 12.6, C-10': 20.4, C-2'- (H 20), mp 141-142C, by acetolysis of
OMe: 55.7 chloroatranorin
MS, m/z 358 (M+,4%), 193 (lOO), 166 (10), 165 StL: Heterodermia neoleucomelaena (1.)Poelt;
(3), 164 (3), 149 (IO) Hypogymnia physodes (1.) Nyl.
StL: Lecania brialmontii (Vain.) Zahlbr. TLC: A: 74, B: 79, B': 73, C: 81, E: 30, P: 60
TLC: RF A: 0.78, B: 0.85, C: 0.82 HPLC: R, 42, R, (SA) 126
Lit: Vinet et al. 1990a; Elix et al. 1993a MC: Pigs. 21A,B,C,D; 22A
Lit: c.P. Culberson 1969; Elix and Norfolk
1975b; Sundholm and Huneck 1981
Chloroatranorin (Chloratranorin)
Cl9Hl7ClOs (408.78)
S-Chloro-4-0-demethylbarbatic acid
(5-Chlor -4-0-demethylbarbatinsaure)
*
9 8'
Cl
Me
1
7
CO-O
*M~' OH C1s H 17 CI0 7 (380.77)
Cl*'to-o~~~
9 8'
5 2 I l' 7' Me Me
H0 4 3 OH 5 6I COOMe
CHO Me
8 9'
HO 3 OH ~COOH
Prisms (CHCI 3-EtOH), mp 208-208.5C Me Me
8 9'
React: KOH yellow, PD yellow, PeCl3 red-brown
UV (MeOH): 213 (4.21), 252 (3.99), 282nm Needles (acetone-MeOH), mp 185-186C (dec.)
(3.94) React: NaOCI red, PeCl3 (EtOH) violet
IR (KBr): 710, 764, 790, 810, 850, 904, 942, 992, UV (MeOH): 218 (4.84), 274 (4.47), 313nm,
1030, 1080, 1115, 1160, 1180, 1270, 1285, 1360, (4.14)
1385, 1408, 1445, 1582, 1650, 3000, 3500 cm-1 IR (KBr): 740, 760, 800, 818, 828, 908, 986, 1090,
IH-NMR (60MHz,CDCI3 ): 2.09 (3H,s,Me-9), 1120, 1158, 1270, 1412, 1460, 1590, 1606, 1650,
2.56 (3H,s,Me-8'), 2.87 (3H,s~Me-9'), 4.05 (3H,s, 3100, 3460 cm-l
7' -COOMe), 6.56 (IH,s,H-5'), 10.42 (IH,s, IH-NMR (60MHz, acetone-d6 ): 2.00, 2.53, 2.70
CHO-8), 12.05, 12.42, 12.60 (3x1H,3xs,3x-HO-) (12H,3xs,4xMe-), 6.67 (IH,s,H-5')
13C-NMR (25.05MHz,CDCI3 ): C-1: 108.9, C-2: 13C-NMR (25.05MHz,DMSO-d 6 ): C-1: 110.7, C-
166.2, C-3: 112.9, C-4: 163.4, C-5: 115.9, C-6: 2: 155.7, C-3: 111.1, C-4: 154.5, C-S: 114.3, C-6:
149.0, C-7: 169.1, C-8: 197.9, C-9: 21.0, C- 133.0, C-7: 167.1, C-8: 9.0, C-9: 13.3, C-1':
1': 116.9, C-2': 162.9, C-3': 110.6, C-4': 152.0, C- 115.8, C-2': 161.5, C-3': 111.8, C-4': 152.1, C-
5': 115.8, C-6': 139.9, C-7': 172.1, C-8': 9.4, C-9': 5': 115.9, C-6': 139.1, C-7': 173.1, C-8': 9.6, C-9':
23.9, C-7'-COOMe: 52.2 22.8
Deriv: Methyl 5-chloro-4-0-demethylbarbatate, 230 (11), 229 (69),228 (84),227 (50), 226 (98),
needles (CHCI3-MeOH), mp 162-164 DC, from 211 (17), 202 (23),200 (73), 198 (55), 197 (23),
5-chloro-4-0-demethylbarbatic acid with 196 (69), 185 (30), 179 (69), 178 (100), 174 (61),
CHzNz at 0 DC in 1 min 173 (58), 172 (69), 171 (66), 169 (69), 163 (46),
StL: not yet found in lichens 152 (69), 150 (76), 137 (67), 135 (46), 124 (76),
Lit: Sundholm and Huneck 1981 123 (69), 122 (67), 121 (76), 107 (61), 105 (53),
104 (46),103 (49), 101 (69)
Deriv: Methyl 3-chlorodivaricatate, prisms
3-Chlorodivaricatic acid
(MeOH), mp 108-109 D C, from 3-chlorodivari-
(3-Chlordivaricatsaure)
catic acid with CH zN2 at 0 DC in 1 min
C21 H Z3 Cl0 7 (422.11) StL: Thelomma mammosum (Hepp in Hartung)
Massal.
3" TLC: A: 56, B': 57, C: 46
Me HPLC: Rr 32
1u 7 ' Lit: Huneck et al. 1980a; Elix et al. 1985c
5 1 CO-O 3 OH
l' 7' 5-Chlorodivaricatic acid
(5-Chlordivaricatsaure)
CZIHz3Cl07 (422.11)
Me
3"/
3'1
Me
Prisms (MeOH-HzO), mp 158-159 DC, 169 DC
(ethylacetate-n-hexane) 1" 7 '
React: FeCl3 (EtOH) violet C[ 1 CO-O 3 OH
UV (MeOH): 220 (4.70), 275 (4.35), 305nm l' 7'
(4.15)
IR (KBr): 680, 750, 798, 810, 830, 904, 966, 990,
1010, 1080, 1108, 1140, 1174, 1202, 1244, 1288,
Melli
1338, 1398, 1420, 1460, 1500, 1558, 1598, 1650,
3
2900, 3000, 3500 cm- 1
IH-NMR (100MHz,acetone-d6 ): 0.96 (6H,t,Me- Needles (MeOH), mp 142-143 DC
3",Me-3 111 ), 1.50-1.93 (4H,m,-CH z-2",-CH2- React: FeCl3 (EtOH) violet
2111), 2.93-3.09 (4H,t,-CH z-1",-CH z-l l11 ), 4.00 UV (MeOH): 213 (4.66), 263 (4.03), 304nm
(3H,s,MeO-4), 6.75 (IH,s,H-5), 6.79 (1H,d, (3.91)
J=2Hz), 6.82 (IH,d,J=3Hz) (H-3',H-5') IR (KBr): 718, 750, 790, 830, 894, 954,1016,1038,
13C-NMR (25.05MHz,acetone-d6 ): C-l: 107.5, 1070, 1108, 1136, 1170, 1212, 1250, 1292, 1306,
C-2: 159.6, C-3: 107.9, C-4: 160.2, C-5: 107.5, 1334, 1370, 1430, 1464, 1598, 1650, 3000, 3150,
C-6: 146.8, C-7: 169.4, C-l": 39.3, C-2": 26.0, C- 3500cm-1
3": 14.5", C-4-0Me: 56.9, C-l': 111.4, C-2': IH-NMR (100MHz,acetone-d6 ): 0.97, 1.00 (2x
165.0, C-3': 109.2, C-4': 154.8, C-5': 116.4, C-6': 3H,2xt,Me-3",Me-3"'), 1.50-1.90 (4H,m,CH 2-
149.1, C-7': 173.1, C-l"': 38.7, C-2"': 25.7, C-3"': 2",-CHz-2"'), 2.94-3.17 (4H,m,-CH 2-1",-CH z-
14.4" (values marked with a may be exchanged) I"'), 3.95 (3H,s,MeO-4), 6.61 (IH,s,H-3), 6.77
MS, m/z 422 (M+,1 %),378 (1),246 (I5), 244 (46), (1H,d,J=2Hz), 6.81 (1H,d,J=2ljz) (H-3',H-5')
3.16 Depsides 243
13C-NMR (25.05MHz,CDCI3 ): C-1: 108.1, C-2: TLC: RF A: 0.42, B: 0.62, C: 0.47

162.3, C-3: 99.6, C-4: 160.3, C-5: 115.6, C-6: Lit: Elix et al. 1988
143.6, C-7: 168.6, C-1": 35.0, C-2": 23.7, C-3 111 :
14.7", C-4' -OMe: 56.8, C-l': 111.0, C-2': 165.1,
I'-Chloronephroarctin
C-3': 109.2, C-4': 155.0, C-5': 116.3, C-6': 149.0,
( 1'-Chlornephroarctin)
C-7': 173.1, C-1111: 38.7, C-2111: 25.6, C-3 111 : 14.4a
(values marked with a may be exchanged) CzoH19CI07 (406.80)
MS, m/z 229 (92%),228 (92), 227 (100), 226 (95),
D::~::---M:~:~
202 (90),200 (97), 179 (87), 174 (88), 172 (93),
171 (92),152 (92), 137 (92),124 (95), 123 (85)
Deriv: Methyl 5-chlorodivaricatate, mp 115-
117C, from 5-chlorodivaricatic acid with
CH1N 1 in Et10 at OC in 1 min eHO Me
StL: Dimelaena cf. radiata (Tuck.) Hale et W.L. Plates (CH1Cl1-n-pentane), mp 181C
Culberson React: PD yellow
TLC: A: 42, B': 62, C: 46 lH-NMR (200MHz,CDCI3 ): 2.22, 2.24, 2.37, 2.75
Lit: Huneck et al. 1980a; Elix et al. 1995e (4x3H,4xs,4xMe-), 3.81 (3H,s,MeO-2'), 10.23,
10.38 (2xlH,2xs,2x-CHO), 13.52, 13.87 (2xlH,
3-Chloroimbricaric acid 2xs,2xHO-)
(3-Chlorimbricarsaure) MS, m/z 406 (M+,O.1 %), 207 (12), 202 (32), 201
(12), 200 (100), 187 (9), 185 (29), 180 (6), 178
C23 H 17 CI0 7 (450.90) (16),165 (12), 159 (15),158 (5),157 (48), 152 (9),
151 (10), 135 (5), 122 (15), 121 (12), 107 (5), 105
(5)
StL: Pseudocyphellaria pickeringii (Tuck.)
D.Gall.
TLC: RF A: 0.69, B: 0.54, C: 0.67
1 eO-O~3' OH HPLC: R1 37
Lit: Elix et al. 1987h
MeO OH " eOOH
,111
3-Chlorostenosporic acid
Me (3-Chlorstenosporsaure)
3'"
C23 H z7CI0 7 (450.90)
Crystals (EtOAc-n-pentane): mp 128-130C 3"
lH-NMR (CDCIJ: 0.74-1.11 (6H,m,Me-5",Me-
M.D~::-D5' 3'
3111 ), 1.20-1.81 (8H,m,-CH z-2"-4",-CH z-2111 ),
2.85-3.15 (2H,2xbt,-CH1-l",-CHz-l l11 ), 3.98
OH
(3H,s,MeO-4), 6.40 (1H,s,H-5), 6.59, 6.72
(2xlH,2xd,J=2.5Hz,H-3',H-5'), 11.60-11.80 eOOH
(2H,bs,HO-,COOH)
MS, m/z 272 (2%),256 (4), 254 (13), 230 (6),228
el
(20),196 (2),178 (9), 174 (32),172 (100), 150 (5)
StL: not yet found in lichens Me
5 111
Crystals (CH 2CI2-n-pentane), mp 138C. Confluentic acid (Confluentinsaure)

IH-NMR (CDCI3): 0.92-1.10 (6H,m,Me-3",Me-
C2sH360S (500.57)
5"'), 1.20-1.80 (8H,m,-CH 2-2",-CH2-2"'-4"'),
3.00, 3.02 (2x2H,2xbt,-CH 2-1",-CH2-1"'), 4.00 7"
(3H,s,MeO-4), 6.46 (1H,s,H-5), 6.55, 6.76 (2H, Me
2xd,J=2.5Hz,H-3',H-5'), 11.45-11.80 (2H,bs,
HO-,-COOH)
MS, m/z 244 (14%),228 (32),226 (100), 224 (8),
206 (14), 169 (27), 150 (22), 124 (22) 7
StL: Dimelaena californica (Magn.) Sheard CO-O OMe
TLC: A: 44, B': 61, C: 49 1 7'
HPLC: Rl 39 eOOH
Lit: Elix et al. 1988
3-Chloroperlatolic acid (3-Chlorperlatolsaure) Me

5 111
C2sH31CI07 (478.95)
Needles (MeOH), mp 15]OC
5/1 React: FeCl3 (EtOH) brown
Me UV (MeOH): 268 (4.18), 304nm (3.86)
IR (KBr): 740, 800, 830, 855, 900, 950, 980, 1040,
1065, 1082, 1115, 1140, 1160, 1205, 1250, 1290,
1330, 1420, 1465, 1500, 1590, 1620, 1660, 1700,
OH 2600,2700,2900,2950,3100, 3500cm-1
IH-NMR (60MHz,CDCI3): 0.90 (6H,m,Me-7",
MeO eOOH
Me-5"'), 1.05-2.00 (12H,m,-CH 2-4"-6",-CH2-
CI 2'" -4"'), 2.20-2.90 (4H,m,-CH 2-3",-CH 2-1 111 ),
3.83, 3.85 (2x3H,2xs,MeO-4,MeO-2'), 4.08 (2H,
Me s,-CH2-1"), 6.30, 6.50, 6.58, 6.61 (4x1H,4xd,
5(// 4xarom.-H)
J3C_ NMR (25.05 MHz,acetone-d6): C-1: 105.6,
Crystals (EtOAc-n-pentane), mp 128C C-2: 166.7, C-3: 100.5, C-4: 165.6, C-5: 113.7,
IH-NMR (CDCI3): 0.70-1.00 (6H,m,Me-5",Me- C-6: 140.9, C-7: 168.4, C-1": 51.3, C-2": 207.0,
5"'), 1.10-1.79 (12H,m,-CH 2-2"-4",-CH 2-2'" C-3": 42.7, C-4": 23.9, C-5": 32.3, C-6": 23.0, C-
-4"'), 2.87, 3.12 (2x2H,2,xbt,-CH 2-1",-CH 2-1"'), 7": 14.3, C-4-0Me: 56.5, C-1': 123.5, C-2': 158.0,
3.99 (3H,s,MeO-4), 6.44 (lH,s,H-5), 6.61, 6.73 C-3': 104.1, C-4': 151.8, C-5': 115.2, C-6': 142.8,
(2H,d,J=2.5Hz,H-3',H-5'), 11.56-11.82 (2H,bs, C-7': 170.2, C-1111: 34.0, C-2"': 31.5, C-3"': 32.0,
HO-,-COOH) C-4"': 23.0, C-5 111 : 14.3, C-2'-OMe: 56.0
MS, m/z 272 (5%), 256 (13), 254 (40), 230 (7), 228 MS, m/z 280 (5%), 266 (20), 263 (25), 262 (97),
(22),206 (11), 174 (31),172 (100) 238 (49), 221 (31),210 (23),206 (41), 195 (11),
StL: Dimelaena californica (Magn.) Sheard 194 (10), 191 (19), 183 (10), 182 (90), 181
TLC: A: 47, B': 66, C: 51 (24), 178 (16), 177 (79), 164 (21), 163 (100), 162
HPLC: R[ 45 (10), 151 (10), 149 (11), 138 (49), 137 (29), 135
Lit: Elix et al. 1988 (31), 123 (13), 106 (13), 77 OS)
3.16 Depsides 245
Deriv: Methyl confluentate, needles (MeOH- (9),67 (5), 65 (10),55 (7),53 (12),51 (7),44 (60),
HzO), mp 123C, from confluentie acid with 43 (6),41 (20)
CHzN z in EtzO at 20C in 1 min StL: Cladonia cryptochlorophaea Asah.
StL: Lecidea confLuens (G.Web.) Ach. TLC: A: 46, B: 46, B': 45, C: 37
TLC: A: 48, B: 32, B': 32, C: 46 HPLC: RJ 23
HPLC: RJ 29 MC: Fig. 23A
MC: Fig. 22B,C,D Lit: C.F. Culberson 1969; Elix and Norfolk 1975a
Lit: Huneck 1962; C.F. Culberson 1969; Elix and
Ferguson 1978; Sundholm and Huneck 1980
Decarboxythamnolic acid
(Decarboxythamnolsaure)
Cryptochlorophaeic acid
(Cryptochlorophaesaure) ClsHl609 (376.31)
CZSH320S (460.51)
*
9 9'
5
Me
11
Me1 to-O~ll.
MeO OH HO~OH
OH eOOH CHO
eo-o 8 8'
HO OMe HO Crystals (acetone), mp 215C (dec.)

3
React: KOH yellow, PD yellow, FeCl3 brown-red
IH-NMR (acetone-d6): 2.28, 2.52 (2x3H,2xs,
Me
5'" 2xMe-), 4.10 (3H,s,MeO-4), 6.40 (lH,s,arom.-
H), 6.69 (1H,s,arom.-H), 10.30 (1H,s,CHO-8')
Needles (benzene), mp 182-184C MS, m/z 299 (71 %),272 (4),209 (9), 191 (73), 168
React: NaOCI purple to red, FeCl3 violet, dis- (14),139 (8), 122 (10), 108 (6),91 (100)
solves in 10% KOH to give first a colourless and Deriv: Methyl decarboxythamnolate, crystals
then a wine-red solution (benzene), mp 163C, from decarboxythamno-
UV (EtOH): 220 (4.6),259 (4.2), 295nm (3.8) lie acid with CHzN z
IR (Nujol): 1580, 1620, 1650, 1735, 3400 cm-l StL: Thamnolia vermicularis (Sw.) Ach. ex
IH-NMR (60MHz,acetone-d6): 0.91 (6H,bt, Schaer.
Me-5/1,Me-5 111 ), 1.22-1.84 (pH,m,-CH z-2/1-4/1, TLC: A: 5, B: 25, B': 18, C: 18, G: 38
-CHz-2111_411f), 3.00 (4H,bt,-CH z-1/1,-CH z-111f), HPLC: Rj 7
3.91 (3H,s,MeO-2), 6.50 (3H,s,H-3,H-5,H-5'), MC: Fig. 35D
8.20 (4H,bs,3xHO-,-COOH) Lit: C.F. Culberson 1969; Pulgarin and Tabacchi
MS, m/z 240 (12%),238 (19), 223 (9),222 (61), 1988
221 (100),207 (10), 196 (23), 195 (5), 194 (10),
182 (35), 181 (7), 179 (7), 178 (5), 177 (20), 166
4-0-Demethylbaeomycesic acid
(5),165 (15), 164 (6), 153 (7), 152 (6),151 (8),140
(4-0-Demethylbaeomycessaure)
(40),139 (56),138 (43),137 (20),123 (8), 122 (5),
121 (6), 107 (6),106 (5),91 (6),79 (5),77 (10),69 ClsHl60S (360.31)
*
9 S' 139.3, C-7: 164.4, C-8: 8.1, C-9: 23.8a, C-1':
Me1 ~o_o*Me OH 115.9, C-2': 161.8, C-3': 111.2, C-4': 151.9, C-5':
116.2, C-6': 138.3, C-7': 173.3, C-8': 9.2, C-9':
l' I 23.1" (values marked with a may be changed)
HO OH 5' tOOH MS, miz 346 (M+,l %),302 (8), 182 (5), 166 (12),
CHO Me 165 (100), 164 (12), 139 (5), 138 (46), 137 (19),
a 9' 136 (16), 123 (13), 109 (6), 107 (5),91 (7),83 (5),
79 (8), 77 (7),63 (5),55 (5),53 (8),43 (6),41 (5)
Fine needles (EtOAc-n-pentane), mp 171-
Deriv: Methyl 4-0-demethylbarbatate, needles
172C
(MeOH), mp 108-111C, from 4-0-demethyl-
React: PD yellow
barbatic acid with CH 2N 2 in Et20 at OC in 30 s
IH-NMR (acetone-d6 ): 2.20, 2.74, 2.82 (3x3H,
StL: Ramalina subdecipiens Stein.
3xs,3xMe-), 6.63, 6.87 (2x1H,2xs,H-5,H-5'),
TLC: A: 39, B: 60, B': 54, C: 36
10.46 (1H,s,CHO-8), 12.65 (lH,bs,HO-)
HPLC: R] 24
MS, miz 316 (0.1), 165 (10), 164 (59), 152 (80),
MC: Figs. 23B,C,D; 24A
150 (52), 138 (50), 136 (91), 106 (21)
Lit: Huneck et al. 1968b; Elix and Norfolk 1975b
StL: Dibaeis arcuatus (Stirton) Gierl et Kalb
TLC: RF A: 0.38, C: 0.30, G: 0.57
Lit: Griffin 1993 4-0-Demethyldiffractaic add
(4-0-Demethyldiffractasaure)
4-0-Demethylbarbatic add C19H2007 (360.3S)
*
(4-0-Demethylbarbatinsaure)
ClsHlS07 (346.32) Me eo_o*Me OH
*
9 S' HO OMe 5' eOOH
Me 7 *Me Me Me
5 1 eo-o OH
Microcrystals (acetone-toluene), mp 207-209C
" 7' IH-NMR (CDCIJ: 2.12, 2.14, 2.36, 2.S8 (4x3H,
HO OH 5' eOOH
4xs,4xMe-), 3.82 (3H,s,MeO-2), 6.51, 6.56
Me Me
a 9' (2X1H,2xs,H-5,H-S'), 9.39 (lH,s,HO-4), 12.62
(lH,s,HO-2')
Needles (MeOH-H 2 0), mp 176-17r (dec.) 13C-NMR (DMSO-d 6 ): C-1: 116.32, C-2: 163.9,
React: NaOCI red, FeCl3 (EtOH) blue-violet C-3: 108.7, C-4: 161.05, C-5: 112.47, C-6:
UV (MeOH): 216 (4.59), 276 (4.32), 306nm 139.96, C-7: 169.2, C-8: 7.93, C-9: 23, C-2-0Me:
(3.96) , 55.68, C-1': 115.18, C-2': 159.91, C-3': 106.67,
IR (KBr): 675, 730, 760, 795, 805, 830, 840, 900, C-4': 149, C-S': 114.01, C-6': 139.4, C-7': 173.1,
1082, 1105, 1140, 1250, 1305, 1410, 1450, 1500, C-8': 9.24, C-9': 22.9
1630, 3100 cm-l MS, miz 360 (M+,0.7%), 316 (0.3), 179 (100), 164
IH-NMR (60 MHz, acetone-d6 ): 2.05, 2.58 (12H, (4), 163 (2), 149 (2), 136 (7), 13S (2)
2xs,4xMe), 6.42, 6.64 (2x1H,2xs,H-5,H-5'), 8.80 StL: Xanthoparmelia duplicata Hale
(2H,bs,HO-,-COOH), 11.56 (1H,s,HO-) TLC: A: 34, B': 44, C: 31
13C-NMR (25.05MHz,DMSO-d6 ): C-1: 103.2, C- HPLC: R] 17
2: 162.5, C-3: 108.7, C-4: 161.0, C-5: 111.2, C-6: Lit: Elix et al. 1989a
3.16 Depsides 247
4-0-Demethylglomellic acid
(4-0-Demethylglomellsaure)
C24H2609 (458.45)
co-O OH
5"
Me
OH COOH
3'
Me
5'"
3
Prisms (MeOH), mp 156C
React: NaOCI red
lH-NMR (CDCI3-acetone-~): 0.83 (3H,t,J=
Me 7Hz,Me-), 0.89 (3H,t,J=6.8Hz,Me-), 1.19-1.69
5'1/
(8H,m,-CH 2-4/1,-CH 2-2"'-4"'), 2.43 (2H,t,J=
7. 1Hz,-CH 2-3/1), 3.01 (2H,t,J=6.5Hz,-CH2-1"'),
Small prisms (MeOH), mp 152C 4.07 (2H,s,-CH 2-1/1), 6.30 (lH,d,J=2.2Hz,H-3),
React: NaOCI red 6.40 (lH,d,J=2.2Hz,H-3'), 6.49 (lH,d,J=2.2Hz,
lH-NMR (CDCI3-acetone-d6): 0.83 (3H,t,J= H-5'), 6.58 (lH,d,J=2.2Hz,H-5)
7.1Hz,Me-), 0.96 (3H,t,J=7Hz,Me-), 1.26-1.69 MS, m/z 224 (2%), 221 (l0), 220 (83), 180 (16),
(4H,m,-CH 2-4/1,-CH 2-4"'), 2.01 (2H,t,J=7.8Hz,- 177 (30), 163 (32), 150 (57), 124 (100), 123 (30),
CH2-3"'), 2.42 (2H,t,J=7.1Hz,-CH z-3/1), 3.40 121 (50), 77 (12), 71 (32), 69 (27), 65 (15)
(2H,s,-CH 2-1"'), 4.05 (2H,s,-CH 2-1/1), 6.30 (lH, StL: Neofuscelia loxodes (Nyl.) Essl.
d,J=2.6Hz,H-3), 6.43 (lH,d,J=2.6Hz,H-5), 6.49 TLC: A: 29, B': 36, C: 21, G: 52
(lH,d,J=2Hz,H-3'), 6.63 (lH,d,J=2.0Hz,H-5') HPLC: R] 20
MS, m/z 238 (8%), 221 (26), 220 (100), 194 (38), Lit: Elix and Whitton 1989
192 (B), 191 (l7), 177 (59), 167 (11), 163 (57),
151 (22), 150 (99),123 (31), 122 (11), 121 (68),77
(l6), 71 (79), 69 (43),65 (30) 4-0-Demethylimbricaric acid
StL: Neofuscelia loxodes (Nyl.) Essl. (4-0-Demethylimbricarsaure)
TLC: A: 22, B': 20, C: 11, G: 48 C22 H 2P7 (402.43)
HPLC: R] 12
Lit: Elix and Whitton 1989
4-0-Demethylglomelliferic acid
(4-0-Demethylglomellifersaure) CO-O 3' OH
C24H2S0S (444.46)
OH ~COOH
Me
Prisms (n-hexane-acetone), mp 108C 124 (68), 123 (52), 122 (11),121 (68),77 (21), 71
React: NaOCI red (44),69 (43),65 (27)
IH-NMR (CDCI3-DMSO-d6 ): 0.97 (6H,m,2x- StL: Neofuscelia loxodes (Nyl.) Essl.
CHz-Me), 1.07-2.00 (8H,m,4x-CH z-), 2.86-3.20 TLC: A: 23, B': 34, C: 18, G: 49
(4H,m,2xbenzyl.-CH z-), 6.33, 6.43 (2H,2xd, HPLC: Rr 14
H-3',H-5'), 6.81 (2H,s,H-3,H-5) Lit: Elix and Whitton 1989
MS, m/z 224 (2%),196 (36), 179 (14),178 (100),
152 (48), 150 (35), l37 (22), 125 (l3), 124 (97),
4-0-Demethylmicrophyllinic acid
123 (51), 122 (19), 121 (32)
(4-0-Demethylmicrophyllinsaure)
StL: Cetrelia sanguinea (Schaer.) W.Culb. et
C.Culb.
TLC: A: 35, B': 57, C: 32
Lit: C.F. Culberson and W.L. Culberson 1976; 7"
Me
Elix et aI. 1985c; Elix and Ernst-Russell 1993
4-0-Demethylloxodellic acid
(4-0-Demethylloxodellsaure) o
HO
C22 Hz4 0 S (416.41)
5"
Me
::-O'((::OH Me
7'"
,/II~ Small prisms (acetone-cyclohexane), mp 162C

React: NaOCI red
Me IH-NMR (CDCI3 ): 0.79 (3H,t,J=7Hz,Me-), 0.9
3'"
(3H,bt,Me-), 1.18-1.58 (6H,m,3x-CH z-), 1.92-
Small prisms (MeOH), mp 146C 2.10 (2H,m,-CH z-3" or 3111 ), 2.43 (2H,t,J=7Hz,-
React: NaOCI red CHz-3" or 3"'), 4.05 (4H,s,-CH z-l",-CHz-1 111 ),
IH-NMR (CDCI3-acetone-d6 ): 0.83, 0.95 (2x3H, 6.20, 6.35 (2xlH,2xd,J=2.5Hz,H-3,H-5), 6.50,
2xt,J=7Hz,2xMe-), 1.26-1.68 (4H,m,-CH z-4",- 6.64 (2xlH,2xd,J=2.5Hz,H-3',H-5'), 10.90 (2H,
CH z--'-2"'), 2.41 (2H,t,J='7.2Hz,-CHz-3"), 2.99 bs,HO-,-COOH)
(2H,t,J=6.3Hz,-CH z-l"'), 4.04 (2H,s,-CH z-l"), MS, m/z 478 (7%), 426 (1), 395 (1),354 (1), 338
6.28 (1H,d,J=2.4Hz,H-3), 6.42 (IH,d,J=2.4Hz, (4),312 (3), 248 (64), 222 (9),192 (47), 150 (100)
H-3'), 6.46 (1H,d,J=2.4Hz,H-5'), 6.58 (IH,d, StL: Parmotrema demethylmicrophyllinicum
J=2.4Hz,H-5) Elix
MS, m/z 310 (1%),221 (19),220 (100), 194 (12), TLC: A: 32, B': 31, C: 16
192 (11), 191 (16), 179 (17), 178 (23), 177 (57), HPLC: Rr 23
163 (56), 152 (39), 151 (10), 150 (72), l37 (14), Lit: Elix and Jayanthi 1987b
3.16 Depsides 249
4-0-Demethylplanaic acid StL: Ramalina americana Hale

(4-0-Demethylplanasaure) TLC: A: 40, B: 41, B': 52, C: 36
Lit: c.P. Culberson et al. 1990a; Elix and Ernst-
CZ6H3409 (458.53)
Russell 1993
5"
M('
4-0-Demethylsphaerophorin
CZZHZ607 (402.43)
8
Me
HO
X:(~O-O OH
HO 3 OH COOH
M(' ,II
5
Needles (MeOH), mp 122-124 DC
IH-NMR (270MHz,CDCl3): 0.89 (6H,t,J=6Hz, Me
Me-5",Me-5"'), 1.60-1.70 (l2H,m,6x-CH z-), 7 '/1
2.66 (2H,t,J=8Hz,-CH z-l"), 2.79 (2H,t,J=8Hz,-
CH z-l"'), 3.86 (3H,s,MeO-2), 3.92 (3H,s,MeO- Needles (CCl4), mp 136 DC
2'), 6.33 (2H,dd,J=2Hz,H-3,H-5), 6.74 (2H,dd, React: NaOCl red
J=2Hz,H-3',H-5') IH-NMR (200MHz,CDCl3-acetone-d6): 0.80-
MS, m/z 458 (M+,0.2%), 238, 221 1.00 (3H,m,Me-7"'), 1.20-1.50 (lOH,m,-CH z-2'"
StL: Lecidea plana (Lahm in Korb.) Nyl. -6"'), 2.61 (3H,s,Me-8), 3.05 (2H,bt,-CH z-l l11 ),
Lit: Huneck and Schmidt 1995 6.40 (2H,s,H-3,H-5), 6.60, 6.74 (2xlH,2xd,J=
2.5Hz,H-3',H-5'), 11.50 (3H,bs,3xHO-)
MS, m/z 340 (0.01%), 208 (12), 150 (5), 137 (10),
4'-0-Demethylsekikaic acid 124 (100), 123 (28)
(4' -0-Demethylsekikasaure) StL: Sphaerophorus melanocarpus (Sw.) DC.
CZIHz40S (404.40) TLC: A: 38, B': 57, C: 33
HPLC: RJ 33
Lit: c.P. Culberson et al. 1985; Elix and Wardlaw
~CO-O~'COOH 1987
4-0-Demethylsquamatic acid
MeO OH HO~ (4-0-Demethylsquamatsaure)
M('
ClsHl609 (376.31)
Pysical data unknown, only micro chemically
identified
React: NaOCl red
MS, m/z 212,210, 193
*
9 8' 4-0-Demethylsuperconfluentic acid
Me1 ~o_o*MeOH (4-0-Demethylsuperconfluentinsaure)

C3,H42 0 S (542.65)
HO 5 OH 5' ' t~OH Me
eOOH Me
8 9'
Microcrystals (acetone), mp 128-130 DC
React: NaOCl red
'H-NMR (acetone-d6-pyridine-ds): 2.50, 2.71,
2.76 (3x3H,3xs,3xMe-), 6.96 (2H,s,H-S,H-S')
MS, m/z 240 (2%), 160 (8), 138 (40), 137 (27),91
(100)
StL: Pertusaria squamatica Archer et Elix
TLC: RF A: 0.03, C: 0.01, C: 0.03
Lit: Griffin 1993
Me
4-0-Demethylstenosporic acid
(4-0-Demethylstenosporsaure) Physical data unknown
React: NaOCl red
C22 H 26 0 7 (402.73) StL: Stirtonia ramosa Makhija et Patwardhan
TLC: RF A: 0.41, B: 0.37, C: 0.30
~CH
HPLC: RT 1.219 (MeOH:H 20:AcOH = 82: 18:
1.6)
3' OH Lit:C.F. Culberson et al. 1990c
HO 3 OH 5' eOOH
3,5-Dichloro-2'-O-methylanziaic acid
(3,5-Dichlor-2'-O-methylanziasaure)
C2sH30C1207 (513.40)
Me
Prisms (n-hexane-acetone), mp 108 DC
React: NaOCl red
'H-NMR (acetone-d6 ): 0.97 (6H,m,2xMe-),
1.17-2.10 (8H,m,4x-CH 2-), 2.73-3.27 (4H,m,
2xbenzyl.-CH2 - ) , 6.37, 6.47 (2H,2xd,J=2.SHz,
Cl eo-O OMe
H-3',H-S'), 6.83 (2H,s,H-3,H-S)
MS, m/z 224 (24%),206 (38), 196 (19), 181 (20), HO OH
178 (63), 168 (22), 163 (16), 150 (61), 137 (14),
Cl
124 (100), 123 (33), 122 (23), 121 (32)
StL: Neofuscelia pokornyi (K6rb.) Essl.
TLC: A: 44,B: 54, C:32 Me
HPLC: Rr 28 5"1
Lit: C.F. Culberson et al. 1977a; Elix et al. Needles (acetone-benzene or MeOH-H2 0), mp
1985c 154-155 DC (dec.)
3.16 Depsides 251
React: NaOCI red, FeCl3 (EtOH) red-brown IH-NMR (270MHz,aceton-d6 ): 2.16 (3H,s,Me-
UV (MeOH): 207.5 (4.78), 276 (4.07), 318nm 8), 2.18 (3H,s,Me-8'), 2.47 (3H,s,Me-9), 2.61
(3.54) (3H,s,Me-9'), 3.85 (3H,s,MeO-2), 387 (3H,
IR (KBr): 700, 750, 774, 808, 840, 920, 964, 990, s,MeO-4), 6.54 (lH,s,H-5), 6,62 (lH,s,H-5'),
1090, 1120, 1148, 1240, 1298, 1380, 1420, 1464, 11.7 (lH,s,HO-2')
1560, 1586, 1646, 1690, 2950, 3460 cm- J !3C-NMR (25.05MHz,DMSO-d6 ): C-1: 119.4, C-
IH-NMR (270MHz,CDCI3): 0.88, 0.90 (2x3H, 2: 159.5, C-3: 116.1, C-4: 156.4 C-5: 108.4, C-6:
2xt,J=6Hz, Me-5",Me-5"'), 1,36 (4H,m,2x- 134.8, C-7: 165.5, C-8: 8.8 C-9: 19.5, C-2-0Me:
CH 2 - ) , 1.66 (4H,m,2x-CH 2 - ) , 2.76 (2H,t,J=8Hz, 61.7, C-4-0Me: 55.7, C-1': 116.5, C-2': 161.7,
-CH2-1"), 3.20 (2H,t,J=8Hz,-CH 2-1"'), 3.90 (3H, C-3': 111.0, C-4': 152.4, C-5': 115.8, C-6': 139.3,
s,2'-OMe), 6.66 (1H,d,J=2Hz,H-3'), 6.71 (1H,d, C-7': 173.4, C-8': 9.0, C-9': 23.0
J=2Hz,H-5'), 11.64 (3H,bs,2xHO-,-COOH) MS, miz 374 (M+,O.l%), 210 (0.1), 194 (13),193
MS, miz 279 (3%),278 (6), 277 (2), 276 (36),275 (100),182 (0.3), 179 (7), 178 (9), 177 (5), 164 (5),
(6),274 (48),238 (84),221 (15),192 (21),182 (l00), 163 (8), 150 (25), 149 (7),148 (5),135 (9), 120 (5),
177 (66), 157 (12), 138 (48), 123 (15), 106 (9) 107 (9), 105 (9), 91 (12), 79 (10), 78 (5), 77 (10),
Deriv: Di -O-acetyl-3,5-dichloro-2'-O-methyl- 44 (8)
anziaic acid, needles (MeOH-H 20), mp 78- Deriv: Methyl diffractate, needles (EtOH), mp
79 DC, from 3,5-dichloro-2'-O-methylanziaic 127-128 D C, from diffractaic acid with CH 2N2 in
acid with Ac2 0-H 2S0 4 Et 20
StL: Lecanora sulphurella Hepp StL: Usnea diffracta Vain.
TLC: A: 43, B': 46, C: 45 TLC: A: 44, B: 64, B': 55, C: 51
HPLC: RJ 32 HPLC: RJ 30
MC: Figs. 62D; 63A,B MC Figs. 24B,C,D; 25A
Lit: Huneck et al. 1977a; Elix et al. 1985c Lit: C.F. Culberson 1969; Elix and Norfolk
1975b; Sundholm and Huneck 1981; Nishitoba
et al. 1987
Diffractaic acid (Diffractasaure)
C2o H 22 0 7 (374.38)
2,2' -Di-O-methylanziaic acid
*co-o
9 8' (2,2'-Di-O-methylanziasaure)
Me 7 Me
OH C26H3407 (458.53)
' 7'
MeO 54 3 2 0Me eOOH
5"
Me Me Me
8 9'
Crystals (benzene), mp 189-190 D C

React: FeCl3 blue
eo-o OMe
UV (MeOH): 214 (4.63), 252 (4.10), 306nm
(3.56) HO OMe eOOH
IR (KBr): 730, 762, 788, 800, 812, 840, 850, 890,
924, 986, 1000, 1030, 1050, 1060, 1090, 1098,
1130, 1178, 1220, 1258, 1316, 1380, 1400, 1460,
1494, 1570, 1630, 1730, 2500, 2920, 3000, 3120, Me
3500cm-1 5'"
Prisms (benzene-cyclohexane), mp lOS-107C, MS, m/z 252 (5%),236 (17),235 (100), 196 (ll)
resolidifying and melting again at 136-137C; 191 (5)
monohydrate, mp 111-113C StL: Ramalina asahinae W.Culb. et C.Culb.
lH-NMR (60 MHz, CDCI3): 0.84-1.00 (6H,m, TLC: A: 50, B: 35, B': 44, C: 51
Me-5", Me-5"'), 1.24-1.83 (l2H,m,6x-CH z-), Lit: Chester and Elix 1978
2.56-2.90 (4H,m,-CH z-1",-CH z-1"'), 3.78, 3.88
(2x3H,2xs,2x-OMe), 6.36 (2H,bs,2xarom.-H),
2,2'-Di-O-methyldivaricatic acid
6.76 (2H,bs,2xarom.-H), 8.60 (2H,bs,HO,
(2,2'-Di-O-methyldivaricatsaure)
-COOH)
MS, m/z 239 (16%),238 (100), 235 (13),221 (24), CZ3H2S07 (416.45)
196 (10), 195 (13), 194 (45), 183 (11), 182 (100),
t
181 (19), 177 (43), 152 (12), 151 (ll), 138 (78), 3"
137 (14)
Me
Deriv: Methyl plan ate, needles (MeOH-HzO), ,,,
mp 58-60C, from 2,2-Di-O-methylanziaic acid
with CHzNz in Etp at 20C in 24h CO-0~31 OMe
StL: Stereocaulon ramulosum (Sw.) Rausch. MeO 5 OMe 51 " COOH
TLC: RFO.32 (n-hexane:EtzO:HCOOH= 13 :8:2) 3 ,'1/
Lit: Cambie 1968; C.F. Culberson 1972b; Elix
1974 Me
3"1
4,4'-Di-O-methylcryptochlorophaeic acid Microcrystals (EtOAc-n-pentane), mp 129-

(4,4' -Di-O-methylcryptochlorophaestiure) 131C
CZ7H360g (488.56) lH-NMR (CDCI 3 ): 0.98, 0.99 (2x3H,2xt,J=8.2Hz,
Me-3",Me-3"'), 1.62-1.74 (4H,m,-CH z-2",-
CH z-2"'), 2.68, 2.80 (2x2H,2xt,J=8.1Hz,-CH 2-
5" 1",-CH z-1"'), 3.85, 3.87, 3.93 (3x3H,3xs,
Me
3xMeO-), 6.39, 6.40 (2X1H,2xd,J=2.4Hz,H-3',
H-5'), 6.74, 6.77 (2x1H,2xd,J=2.2Hz,H-3,H-5)
OH MS, m/z 223 (0.1%),208 (14),207 (100),192 (1),
CO--O 178 (2), 177 (2), 164 (1) 151 (1), 135 (4)
StL: Pertusaria subplanaica Archer et Elix
MeO OMe MeO TLC: RF A: 0.39, B: 0.24, C: 0.44
3
Lit: Archer and Elix 1992; Elix et al. 1993a
2,2'-Di-O-methylimbricaric acid
(2,2' -Di-O-methylimbricarsaure)
Crystals (benzene-cyclohexane), mp 147-148 C
lH-NMR (l00 MHz,acetone-d6 ): 0.85 (6H,bt, CZS H 32 0 7 (444.51)
2xMe-), 1.19-1.90 (12H,m, 6x-CH z-), 2.61-3.10
(4H,m,-CH z-1",-CH z-1 111 ), 3,79, 3.81, 3.92
(3x3H,3xs,3xMeO-), 6.45, 6.60 (2x1H,2xd,J=
2Hz,H-3,H-5), 6.45 (lH,s, H-5')
3.16 Depsides 253
1:
3" (2x3H,2xs,2x-OMe), 6.44, 6.67 (2XIH,2xd,J=
2Hz,H-3,H-5), 6.44 (1H,s,H-5')
MS, mlz 226 (36%), 210 (39),209 (16),208 (97),
OMe 193 (75), 192 (15), 190 (20), 182 (17), 179 (39),
co - o 178 (16), 177 (73), 166 (41), 163 (21), 162 (60),
MeO OMe eOOH 152 (36), 151 (40), 138 (100), 137 (39), 136 (16),
134 (33),123 (17), 121 (15), 107 (16),95 (13),91
(23),84 (12), 79 (19), 78 (16),77 (32), 69 (27),67
(15),65 (24),55 (15), 53 (20),51 (21),44 (68), 43
Me (15)
5 111 StL: Ramalina asahinae W.Culb. et C.Culb.
TLC: A: 32, B: 29, B': 27, C: 18
Crystals (EtOAc), mp 137-138C
HPLC, R] 16
IH-NMR (CDCI3): 0.91, 0.95 (2x3H,2xt,J=
Lit: Chester and Elix 1978
7.4Hz,Me-3",Me-5 111 ) , 1.34, 1.66 (8H,2xm,-
CHz-2",-CHz-2111-4111 ), 2.70 (2H,t,J=6.9Hz,-CHz-
1"), 2.80 (2H,t,J=7.7Hz,-CH z-l l11 ) , 3.85, 3.87, 2,2' -Di-O-methylstenosporic acid
3.93 (3x3H,3xs,3x-OMe), 6.38, 6.40 (2xlH, (2,2' -Di-O-methylstenosporsaure)
2xd,J=2.2Hz,H-3',H-5'), 6.74, 6.78 (2xlH,
2xd,J=2Hz, H-3,H-5) CZSH3Z07 (444.51)
MS, m/z 236 (14%),235 (100), 151 (4), 135 (2)
StL: Pertusaria subplanaica Archer et Elix 5"
Me
TLC: Rf A: 0.42, B: 0.29, C: 0.46
J
2,4'-Di-O-methylnorsekikaic acid eo-o 3 OMe

(2,4' -Di-O-methylnorsekikasaure)
C22 Hz 6 0 S (418.43)
3 OM_ ~COOH
1:
3" Me
Me 3'"
Needles (EtOAc-n-hexane), mp 135C

CO - O*COOH IH-NMR (CDCI3): 0.89, 0.99 (2x3H,2xt,J=
6.9Hz,Me-5",Me-3 111 ), 1.24-1.75 (8H,m,-CH z-
HO 3 OMe Meo~ 2"-4",-CH z-2 111 ), 2.69, 2.80 (2x2H,2xt,J=7.8Hz,
Me -CH z-l",-CHz-l l11 ) , 3.85, 3.87, 3.93 (3x3H,3xs,
3'" 3x-OMe), 6.39, 6.40 (2XlH,d,J=2Hz,H-3',H-5'),
6.74, 6.77 (2xlH,d,J=2Hz,H-3,H-5)
Pale yellow crystals (acetone-benzene-cyclohex- MS, mlz 244 (1 %),208 (IS), 207 (100), 192 (1),
ane), mp 132-134C 191 (1), 177 (3), 164 (1), 151 (2)
IH-NMR (100MHz,acetone-d6 ): 0.98 (6H,bt, StL: Pertusaria subplanaica Archer et Elix
Me-3",Me-3 111 ) , 1.51-1.91 (4H,m,-CH z-2",2 111 ), TLC: RF A: 0.44, B: 0.29, C: 0.48
2.65-3.13 (4H,m,-CH z-l",-CHz-l l11 ) , 3.84, 3.96 Lit: Archer et Elix 1992; Elix et ai. 1993a
Diploschistesic acid (Diploschistessatire) Needles (benzene), mp 13 7-138 DC

React: PeCl3 violet
Cl6Hl40S (334.27)
UV (MeOH): 213 (4.56), 269 (4.16), 306nm
~co-oyyO"
(3.94)
IR (KBr): 690, 710, 730, 760, 800, 830, 875, 900,
960, 980, 1020, 1044, 1075, 1140, 1150, 1200,
HO~OH ~eOOH 1220, 1235, 1280, 1300, 1308, 1350, 1425, 1460,
OH Me 1605,1640, 1660,2900,3000,3100, 3500cm-1
Needles (acetone-HzO-acetic acid), mp 174 DC MS, m/z 370 (8%), 193 (100), 179 (10), 164 (12),
(dec.) 152 (6), 138 (20), 135 (18), 124 (8), 107 (5)
React: NaOCI red, KOH yellow, Ba(OH)z (in Deriv: Methyl divaricatate, needles (MeOH), mp
HzO) blue, PeCl3 violet 76 DC, from divaricatic acid with CHzNz
UV (MeOH): 212, 270, S 300nm StL: Evernia divaricata (L.) Ach.
IR (KBr): 700, 740, 790, 810, 835, 890,1000,1050, TLC: A: 39, B: 75, B': 68, C: 51
1080, 1150, 1170, 1210, 1250, 1320, 1380, 1410, HPLC: Rr 33
1465,1615, 1650,3150, 3550cm-1 MC: Pig. 25C
MS, m/z 279 (5%), 184 (35),166 (100), 138 (20), Lit: c.P. Culberson 1969
110 (20)
Deriv: Tetraacetyldiploschistesic acid, prisms Elatinic acid (Elatinsaure)
(benzene), mp 164-165 DC, from diploschistesic
acid with AC zO-HzS0 4 CZOHZ009 (404.11)
StL: Diploschistes scruposus (Schreb.) Norm.
TLC: A: 21, B: 39, B': 37, C: 13
HPLC: Rr 10
Diploschistesic acid has an infrared spectrum ~CO-O~OH
and an RF value very similar to that oflecanoric
acid, from which it can easily be differentiated
MeO~OH Y'eOOMe
eOOH Me
by its yellow colour reaction with bis-diazotized
benzidine on the TLC plate. Lecanoric acid
gives a deep red colour with bis-diazotized ben- Needles (EtOAc), mp 212 DC
zidine lH-NMR (CDCI3-acetone-d6 ): 2.08, 2.43, 2.50
MC: Pig. 25B (3x3H,3xs,3xMe-), 3.91, 3.93 (2X3H,2xs,OMe,-
Lit: C.P. Culberson 1969 COOMe), 6.64,6.67 (2H,2xs,H-5,H-5'), 10.92
(1H,s,HO-)
MS, m/z 404 (M+,0.04%), 209 (8), 196 (26), 193
Divaricatic acid (Divaricatsaure)
(18), 191 (27), 190 (10), 165 (25), 164 (100), 163
C21 H 24 0 7 (388.40) (8), 137 (9), 136 (92), 135 (15), 134 (5), 121 (11),
Me 108 (9), 107 (13), 106 (5)
StL: Loxospora elatina (Ach.) Massal.
TLC; RF A: 0.32, B: 0.27, C: 0.43
eo-o OH
Lit: c.P. Culberson et al. 1986; Elix et al. 1989a
Erythrin
Me CZOHZZOll (438.38)
3.16 Depsides 255
it
8 IR (KBr): 690, 715, 785, 804, 830, 842, 882, 950,
Me 7 3' 975, 995, 1020, 1030, 1052, 1080, 1160, 1210,
1 CO-O OH H H
HO
5
3 OH
~
5'(-
'7' ,.. 2"13"14"
CO-O-CH2-C-C-CH20H
1 I
1260, 1300, 1345, 1382, 1420, 1445, 1465, 1510,
1570, 1610, 1650,3050,3120, 3550cm-1
Me OH OH IH-NMR (270 MHz, acetone-d6): 2.64 (3H,s,Me-
8' 8), 2.65 (3H,s,Me-8'), 3.87 (3H,s,MeO-4), 6.41
(lH,d,J=2.47Hz,H-5), 6.47 (lH,d,J=2.44Hz,H-
Needles (MeOH), mp 156-157C, [a]D + 8.0 3), 6.74 (lH,d,J=2.47Hz,H-3'), 6.82 (lH,d,J=
React: NaOCl red, FeCl3 dark purple 2.47Hz,H-5'), 11.17 (lH,s,-COOH)
UV (MeOH): 215 (4.34), 271 (4.03), 307nm 13C-NMR (25.05MHz,DMSO-d6): C-1: 109.9, C-
(3.79) 2: 160.2, C-3: 99.2, C-4: 162.6, C-5: 108.7, C-6:
IR (KBr): 700, 760, 795, 805, 850, 890, 922, 970, 140.4, C-7: 167.1, C-8: 21.5, C-4-OMe: 55.3, C-
1000, 1022, 1052, 1080, 1150, 1170, 1200, 1260, I': 116.1, C-2': 159.6, C-3': 107.7, C-4': 152.6, C-
1305, 1370, 1420, 1455, 1582, 1605, 1650, 3000, 5': 115.1, C-6': 140.2, C-7': 171.1, C-8': 21.5
3350cm-1 MS, m/z 332 (M+,O.4%), 168 (34), 165 (75), 164
13C-NMR (25.05MHz,acetone-d6): C-1: 104.6, (86), 136 (44)
C-2: 164.0, C-3: 101.7, C-4: 166.6, C-5: 112.8, Deriv: Methyl evernate, prisms (EtOH), mp
C-6: 144.6, C-7: 170.2, C-8: 24.4, C-1': 112.5, C- 140C, from evernic acid with CH1N1 in Et20 at
2': 163.6, C-3': 109.3, C-4': 154.6, C-5': 117.2, C- 20C in 30s
6': 143.9, C-7': 171.3, C-8': 23.7, C-1": 68.4, StL: Evernia prunastri (L.) Ach.
C-2": 70.4, C-3": 73.1, C-4": 64.4 TLC: A: 38, B: 61, B': 60, C: 43
Deriv: Hexaacetylerythrin, needles (EtOH), mp HPLC: R126
82-85C, from erythrin with Ac 20-H 2S04 MC: Fig. 26A
StL: Roccella phycopsis Ach. Lit: Robertson and Stephenson 1932; C.F.
TLC: A: 4, B: 5, B': 2, C: 1 Culberson 1969; Sundholm and Huneck 1980;
HPLC: R] 7 Nishitoba et al. 1987
MC: Fig. 25D
Lit: C.F. Culberson 1969; Sundholm and Huneck
1980 Evernin
C19H2007 (360.35)
Evernic acid (Evernsaure)
it
8 8'
C17H1607 (332.30) Me Me-
, 7
CO-O 3" 2 OH
5 ,
it ~E? 4 " 7'

7 3' MeO 3 OH 5' 6' COOMe
5 ' CO-O OH
~COOH
Me
" 7' 9'
Mea 3 OH
Crystals (MeOH), mp 112-114C
Me
8' UV: 221, 265, 305 nm
IR (KBr): 820,1090,1140,1170,1225,1255,1430,
Needles (acetone), mp 172-174C 1560, 1600, 1640,2840, 2940cm-1
React: FeCl3 red IH-NMR (60MHz,CDCIJ: 2.13 (3H,s,Me-8'),
UV (MeOH): 214 (4.81), 269 (4.48), 306nm 2.57 (3H,s,Me-9'), 2.68 (3H,s,Me-8), 3.85 (3H,
(4.23) s,MeO-4), 3.99 (3H,s,-COOMe), 6.42 (2H,s,
H-3,H-5), 6.58 (1H,s,H-5'), 11.50 (lH,s,HO- TLC: A: 15, B: 12, C: 8

2'), 11.97 (lH,s,HO-2) Lit: C.F. Culberson et al. 1987
13C-NMR (22.63MHz,CDC13): C-1: 104.3, C-2:
162.9, C-3: 99.0, C-4: 164.9, C-5: 111.9, C-6:
Glomellic acid (Glomellsaure)
143.5, C-7: 169.9, C-4-0Me: 55.4, C-1': 116.4,
C-2': 152.6, C-3': 110.1, C-4': 166.7, C-5': 116.9, CZSHZS09 (472.47)
C-6': 139.7, C-7': 172.3, C-8': 9.3, C-9': 24.7, C-
5/1
7' -COOMe: 52.1 Me
MS, m/z 360 (M+,8.5%), 196 (15), 166 (35), 165
(100), 164 (48), 149 (10), 137 (6), 136 (52), 135
(9),121 (5), 109 (14), 108 (7), 107 (13), 94 (8), 93
3'
(7), 79 (18), 78 (8), 77 (20), 67 (11), 55 (14), 39 CO- 0 ",-//''--' OH
(18)
StL: Evernia prunastri (1.) Ach. OH
3
TLC: A: 74, B': 71, C: 81, E: 60
HPLC: RJ 39
MC: Fig. 66A
Lit: Nicollier and Tabacchi 1976; Nicollier et al. Me
5'"
1978
Needles (MeOH), mp 135-138C
React: KOH + NaOCl red, FeC13 (EtOH) violet
Glaucophaeic acid (Glaucophaesaure)
UV (MeOH): 215 (4.58), 258 (4.19), 308nm
C34H4609 (598.71) (3.97)
IR (KBr): 690, 720, 764, 808, 858, 900, 920, 990,
Me 1040, 1060, 1078, 1140, 1160, 1180, 1204, 1260,
1290, 1360, 1430, 1450, 1504, 1570, 1610, 1668,
3000, 3450 cm- 1
IH-NMR (CDClJ: 0.83 (3H,t,J=7.3Hz,Me-5" or
Me-5"'), 0.98 (3H,t,J=6.8Hz,Me-5" or Me-5"'),
1.30-1.69 (4H,m,2x-CH z-), 2.03 (2H,t,J=7.8Hz,-
CO-O CH z-3"'), 2.39 (2H,t,J=7.3Hz,-CHz-3"), :;3.20
(2H,s,-CH z-1"') 3.83 (3H,s,-OMe-4), 4.03 (2H,
OMe s,-CHz-1"), 6.28 (1H,d,J=2.5Hz,H-3), 6.44 (1H,
d,J=2.0Hz,H-3'), 6.48 (1H,d,J=2.5Hz,H-5), 6.63
(1H,d,J=2.0Hz,H-5'), 11.1 (3H,bs,3x-OH)
MS, m/z 235 (13%),234 (91), 220 (17),206 (10),
205 (10), 191 (37), 177 (36), 165 (12), 164 (92),
163 (11), 150 (83), 135 (36), 121 (14),92 (10), 77
(1O), 71 (100),69 (24),65 (12),63 (10),55 (10),53
Me
(12), 51 (12)
Physical data unknown, only micro chemically Deriv: Methyl glomellate, needles (MeOH), mp
identified 152-153C, from glomellic acid with CHzNz at
StL: Pseudobaeomyces pachycarpa (Milll. Arg.) OC in 1 min
Sato StL: Neofuscelia verruculifera (Nyl.) Essl.
3.16 Depsides 257
TLC: A: 34, B: 30, B': 27, C: 33 MS, m/z 235 (100%), 234 (100), 224 (12), 207
HPLC: Rr 18 (23),206 (35), 205 (10), 191 (38), 180 (12), 178
Lit: Huneck and Follmann 1973; Elix and (13), 177 (32), 168 (15), 165 (12), 164 (85), 163
Whitton 1989 (14), 150 (46), 137 (11), 135 (36), 124 (67), 123
(20),122 (15), 121 (13),77 (12), 71 (31),69 (28),
65 (11)
Glomelliferic acid (Glomellifersaure)
Deriv: Glomellin, prisms (EtOH), mp 85C, on
C2sH300S (458.49) treatment of glomelliferic acid with KOH in
H 20
StL: Neofuscelia verruculifera (Nyl.) Essl.
TLC: A: 43, B: 47, B': 47, C: 50
HPLC: Rr 27
MC: Fig. 26B,C,D
Lit: C.F. Culberson 1969; Sundholm and Huneck
......................_/OH 1980; Elix and Whitton 1989
Haemathamnolic acid (Haemathamnolsaure)

Cl9H16010 (404.32)
MI?
5 111
Arco_O*Me eOOH
Needles (benzene), mp 143-145C
React: KOH + NaOCl rose or red, FeC13 violet MeO~OH HO OH
UV (MeOH): 218, 268 (4.17), 306nm (4.11) CHO CHO
IR (KBr): 700, 745, 785, 860, 890, 970,1050,1068,
1088, 1150, 1170, 1215, 1250, 1310, 1330, 1420, Pale yellow laths (acetone), mp 202-204C
1440, 1470, 1615, 1660, 1700, 3000, 3100, (dec.)
3500cm-1 React: KOH yellow, PD yellow
IH-NMR (CDC1 3 -acetone-d6): 0.84 (3H,t,J= UV (EtOH): 222 (4.50),283 (4.39), 351 nm (3.82)
6.9Hz,Me-5"'), 0.89 (3H,t,J=6.2Hz,Me-5"), 1.26- IR (KBr): 690, 745, 770, 810, 850, 890, 928, 960~
1.73 (8H,m,4x-CH 2 -), 2.42 (2H,t,J=7.2Hz,-CH2- 980, 1026, 1045, 1062, 1140, 1220, 1250, 1300,
3"), 3.01 (2H,t,J=8.2Hz,-CH2-1"'), 3.84 (3H,s, 1360, 1380, 1395, 1420, 1450, 1630, 1730, 2600,
MeO-4), 4.07 (2H,s,-CH 2-1"), 6.30 (lH,d,J= 2950, 3440 cm-1
2.6Hz,H-3), 6.45 (lH,d,J=6.4Hz,H-5), 6.48 (lH, Deriv: Methyl tri-O-methylhaemathamnolate,
d,J=2.5Hz,H-3'), 6.59 (lH,d,J=2.5Hz,H-5') needles (EtOAc-n-pentane) mp 130-132C,
13C-NMR (25.05MHz, acetone-d6): C-1: 105.6, from haemathamnolic acid with CH3J and
C-2: 116.6, C-3: 100.5, C-4: 165.7, C-5: 113.6, K2 C0 3 in acetone under reflux in 24h
C-6: 140.8, C-7: 169.7, C-1": 51.3, C-2": 207.0, IH-NMR (60MHz,DMSO-d6) of methyl tri-O-
C-3": 44.6, C-4": 17.5, C-5": 14.0, C-4-0Me: methylhaemathamnolate: 2.25, 2.53 (2x3H,
56.0, C-1': 111.2, C-2': 164.9, C-3': 109.3, C-4': 2xs,2xMe), 3.30 (3H,s,-COOMe), 3.85, 3.87,
154.6, C-5': 116.4, C-6': 149.2, C-7': 173.1, 3.93,4.96 (4x3H,4xs,4x-OMe), 7.04 (lH,s,H-5),
C-l"': 36.7, C-2"': 32.6, C-3"': 32.3, C-4"': 23.1, 10.28, 10.30 (2x1H,2xs,2x-CHO)
C-5"': 14.3 MS, m/z 360, 210, 193, 191
StL: Pertusaria rhodesiaca Vain. 8-Hydroxybarbatic acid

TLC: A: 18, B: 35, B': 34, C: 32, G: 49 (8-H ydroxybarbatinsaure)
HPLC: RI 26
Cl9HzoOs (376.35)
MC: Pig. 27B,C,D
Lit: c.P. Culberson 1969 Me Me
Homosekikaic acid (Homosekikasaure)

C24H300S (446.48)
MoO~::-O~::OH
CH20H Me
3" a
~,,, Crystals (EtOAc-cyclohexane), mp 192-194C

OH IH-NMR (CDCI3): 2.10, 2.52, 2.63 (3x3H,
:(j(CO-O
3xs,3xMe-), 3.86 (3H,s,MeO-4), 4.72 (2H,s,-
CHzOH-8), 6.35, 6.47 (2x1H,2xs,H-5,H-5'),
MeO 3 OH MeO 11.64, 11.86 (2x1H,2xs,2xHO-)
MS, mlz 182 (7%), 177 (6),166 (5),164 (36),162
(4),152 (5),150 (7),149 (11),147 (5),141 (5), 139
(4), 138 (33), 137 (20), 136 (53), 135 (13), 123
(15), 121 (10), 59 (100)
Prisms (benzene-n-pentane), mp 133-13rC StL: Xanthoparmelia moctezumensis Nash
React: PeCl3 violet TLC:A:20,B:29,C:24
IR (KBr): 710, 740, 840, 910, 965, 988,1040,1090, Lit: c.P. Culberson et a1. 1979, 1990a; Elix et a1.
1130, 1158, 1202, 1224, 1250, 1320, 1350, 1385, 1993a
1430, 1460, 1510, 1580, 1620, 1640, 3000,
3500 cm-I
8-Hydroxydiffractaic acid
IH-NMR (60MHz,CDCI3): 0.94 (6H,bt,2xMe-), (8-Hydroxydiffractasaure)
1.25-1.90 (8H,m,4x-CH z-), 3.02 (4H,bt,-CH 2-
1",1"'),3.82,3.89 (2x3H,2xs,2x-OMe), 6.39 (2H, CZOH 22 0 S (390.38)
s,H-3,H-5), 6.47 (1H,s,H-5'), 11.20 11.52 (3H,
2xbs,2xHO-,-COOH)
MS, m/z 446 (M+,O.l%), 358 (2),254 (23), 237
(10),236 (65),218 (3), 211 (6),210 (46), 193 (19),
192 (100),190 (4),179 (8),177 (5),164 (19),136
(5), 135 (23), 134 (5), 91, (5), 79 (5), 78 (5), 77
(10),69 (7), 65 (5), 55 (5), 53 (7),51 (7),49 (10),
42 (5)
Deriv: Methyl homosekikate, crystals, mp Crytals (EtOH), mp 156-158C
106C, from homosekikaic acid with CHzN z IR (KBr): 1655, 1735, 3450cm-1
StL: Cladonia ramulosa (With.) Laund. IH-NMR (270MHz,acetone-d6 ): 2.13 (3H,s,Me-
TLC: A: 45, B: 69, B': 65, C: 56 9'), 2.47 (3H,s,Me-8'), 2.63 (3H,s,Me-9), 3.91
HPLC: RI 35 (3H,s,MeO-2), 3.97 (3H,s,MeO-4), 4.66 (2H,s,-
MC: Pig. 28B CHz-OH-8), 6.65 (1H,s,H-5), 6.82 (1H,s,H-5')
Lit: c.P. Culberson 1969; Elix and Norfolk StL: Usnea longissima Ach.
1975a Lit: Nishitoba et a1. 1987
3.16 Depsides 259
5-Hydroxylecanoric acid 5"

(5-H ydroxylecanorsaure) Me
CI6HI40S (334.27)
OH
ME'
CO-O*OOH
HO~CO-O~OH
Mea OH Mea 5' ,//
HO.Nl.OH ,\""COOH 3
. Me
ME' 3'1/
Physical data unknown Plates (EtOAc-n-pentane), mp 125-126C

React: NaOCI red IH-NMR (CDCI3): 0.85, 0.91 (2x3H,2xt,J=6.9,
MS, m/z 334 (M+), 184, 168, 150 7.0Hz,Me-5",Me-3"'), 1.53-1.78 (6H,m,3x-
StL: not yet found in lichens CH 2-), 2.57, 3.02 (2x2H,2xt,J=7.3,8.7Hz,-CHz-
TLC: A: 21, B: 36, B': 33, C: 11 1",-CH 2-1 111 ), 3.83, 3.90 (2x3H,2xs,MeO-4,
Lit: Elix and Ernst-Russell 1993 MeO-4'), 6.36, 6.40 (2xlH,2xd,J=2.8Hz,H-3',
H-5'), 6.45 (1H,s,H-5), 11.20,11.52 (2xIH,2xs,
2xHO-)
Hyperconfluentic acid
MS, m/z 238 (24%),236 (24),221 (11),220 (44),
(Hyperconfiuentinsaure)
192 (22), 181 (11), 182 (33), 179 (11), 177 (16),
C30H400S (528.26) 165 (12), 164 (100), 154 (11), 153(19), 138 (30),
135 (31)
StL: Physcidia wrightii Tuck.
TLC: A: 56, B': 64, C: 61
HPLC: Rr 38
Lit: c.P. Culberson et al. 1985, 1990a; Elix et al.
co-O 1993a
Hyperlatolic acid (Hyperlatolsaure)

C27 H 360 7 (472.55)
5"
Me
Physical data unknown, ot;lly micro chemically

identified. ,
StL: Pseudobaeomyces pachycarpa (Mull.Arg.) co-o ~,3~
Sato
TLC: A: 49, B: 45, C: 60 Me a OH
3
Lit: C.P. Culberson et al. 1987
Hyperhomosekikaic acid
(Hyperhomosekikasaure)
Me
C26 H 3Ps (474.53) 7'/1
Rosettes of crystals (cyclohexane), mp 113 c TLC: RF A: 0.51, B: 0.44, C: 0.59

'H-NMR (200MHz,CDCI3 ): 0.67-1.05 (6H,m, HPLC: R] 0.51
Me-5",Me-7"'), 1.05-1.90 (16H,m,8x-CH 2-), Lit: Elix et al. 1994b
2.77-3.20 (4H,m,-CHz-l",-CH z-l"'), 3.85 (3H,s,
MeO-4), 6.43 (2H,d,H-3,H-5), 6.69, 6.71 (2xlH,
Hyponephroarctin, NA-3
2xd,J=2.5Hz,H-3',H-5'), 10.92 (1H,s,HO-)
MS, m/z 445 (1%),454 (6), 238 (1), 235 (9),222 CZOHZ206 (358. 38)
(14), 221 (100), 220 (10), 192 (5), 164 (15), 138
(10), 137 (6), 124 (20), 123 (5) 10 7'
StL: Rhopalospora viridis (T0nsb.) T0nsb. ME' ME'
TLC: A: 53, B': 74, C: 52
HPLC: R, 54
OH~*' to-O*',OMe
Lit: C.F. Culberson et al. 1984; Elix and Wardlaw HO OH ME' 1
1987 Me
8
8'
ME'
9'
Hyperplanaic acid (Hyperplaasaure)

Needles, mp 165-170C
CZ9H4007 (500.61) React: N aOCI red, PD yellow
UV (CHCI3 ): 263nm (4.59)
5" IR (KBr): 820,1060,1110,1130,1200,1420,1500,
ME'
1630, 1650,2950, 3400 cm-l
'H-NMR (400MHz,CDC}J: 2.03 (6H,s), 2.13,
2.32, 3.00 (3x3H,3xs) (5xMe-), 3.84 (3H,s,
MeO-), 6.67 (lH,s,H-l'), 10.36 (lH,s,HO-),
1 eo-o 12.32, 13.23 (2xlH,2xs,2x-CHO)
I3C-NMR (100MHz,CDCI3 ): 7.2, 9.7, 12.6, 16.8,
ME'O
3
oME'
20.4, 55.8 (OMe), 105.5, 110.6, 113.8, 116.0,
120.0, 135.6, 147.9, 156.0, 166.4, 167.4, 170.1,
194.2
MS, m/z 358 (M+,17%), 193 (100), 166 (87), 151
(12), 135 (3), 83 (3)
ME' StL: Nephroma arcticum (1.) Torss.
7"1 Lit: Kinoshita et al. 1994b
Crystals (cyclohexane-EtQAc), mp 128C
'H-NMR (CDCI3 ): 0.87, 0.89 (3x3H,2xt,J= Hypothamnolic acid (Hypothamnolsaure)
6.9Hz,Me-5",Me-7"'), 1.20-1.66 (16H,m,-CH z-
C19HISOIO (406.33)
2",-4",-CH2-2'" -6"'), 2.70 (2H,t,J=7.9Hz,-CH2-
1"), 2.83 (2H,t,J=7.8Hz,-CH2-1"'), 3.85, 3.87,
3.93 (3x3H,3xs,3x-OMe), 6.38, 6.42 (2xlH,
2xd,J=1.9Hz,H-3, H-5), 6.75, 6.78 (2xlH,2xd, ~CO_O*Me eOOH
J=2Hz,H-3',H-5')
MS, m/z 236 (15%),235 (100) MeO~OH HO OH
StL: Lecanora planaica Lumbsch eaOH Me
3.16 Depsides 261
Needles (acetone), mp 225-22rC (dec.) OMe), 6.41 (2H,s,H-3,H-5), 6.67, 6.80 (2x2H,
React: KOH purple, NaOCI red, PeCl3 purple 2xd,J=2Hz,H-3,H-5,H-3',H-5'), 11.16 (bs,
MS, m/z 362 (2%),318 (4),226 (2),209 (12), 198 HO-,-COOH)
(2), 191 (32), 182 (14), 180 (6), 166 (11), 165 MS, m/z 238 (31%),220 (41), 196 (39),192 (13),
(100), 164 (35), 155 (6), 154 (58), 153 (16), 152 182 (31), 179 (13), 178 (100), 177 (10), 164 (49),
(8), 139 (10), 138 (21), 137 (10), 136 (20), 135 (9), 150 (29), 135 (16), 122 (25), 121 (44),79 (13), 77
125 (7), 121 (14), 109 (12), 108 (15), 107 (13),95 (20),69 (31), 65 (19), 56 (29), 55 (17),53 (11),44
(7),94 (5),93 (9),80 (8), 79 (13),78 (6), 77 (19), (58),43 (14)
71 (7),69 (9), 67 (13),66 (7), 65 (10), 57 (13), 55 StL: Cetrelia cetrarioides (Del. ex Duby) W.Culb.
(12), 53 (10), 52 (5), 51 (9),44 (100), 41 (14) et C.Culb.
Deriv: Dimethyl hypothamnolate, needles (ben- TLC: A: 42, B: 75, B': 71, C: 50
zene), mp 197-198 c, from hypothamnolic acid HPLC: Rj 34
with an equivalent amount of CH 2N z at -15 in MC: Pig. 29A
1 min Lit: c.P. Culberson 1969; Elix 1974
StL: Cladonia pseudostellata Asah.
TLC: A: 4, B: 25, B': 18, C: 23, G: 34
Isohyperlatolic acid (Isohyperlatolsaure)
HPLC: Rj 15
MC: Pig. 28C,D C27H3607 (472.55)
Lit: c.P. Culberson 1969; Elix and Norfolk 1975c
Imbricaric acid (Imbricarsaure)

C23 H zs 0 7 (416.45)
CO-O OH
MeO OH eOOH
3
CO-0~3' OH
OH 5' eOOH
1/1
Me
5'11
Me
3'"
Prisms (cyclohexane), mp 103C
IH-NMR (200MHz,CDCI3): 0.77-1.07 (6H,m,
Needles (benzene-n-pentane or cyclohexane), Me-7",Me-5"'), 1.07-1.80 (16H,m,8x-CH 2-),
mp 125-126C 2.78-3.22 (4H,m,-CH 2-1",-CH2-1"'), 3.83 (3H,
React: FeCl3 (EtOH) violet s,MeO-), 6.38 (2H,s,H-3,H-5), 6.63, 6.77 (2H,
UV (EtOH): 212 (4.67), 269.5 (4.28), 305 nm 2xd,J=2.5Hz,H-3',H-5'), 11.00 (bs,-OH)
(4.07) MS, m(z454 (3%), 267 (5),266 (33), 249 (12),248
IR (Nujol): 1615, 1650, 1670cm-1 (41),224 (35), 222 (17),207 (10), 206 (64), 205
IH-NMR (60MHz,CDCl3): 0.79-1.06 (6H,m,Me- (7),192 (7), 192 (26), 191 (16), 183 (7), 182 (71),
5",Me-3"'), 1.23-1.83 (8H,m,4x-CH z-), 2.91- 181 (8), 180 (18), 179 (6), 178 (29), 177 (32),168
3.08 (4H,m,-CH c 1",-CH2-1"'), 3.83 (3H,s,- (29), 165 (10), 164 (76), 163 (20), 151 (24), 150
(69),149 (9), l39 (9), l38 (100), l37 (28), l36 (8), 8
~Llo-o
135 (16), 125 (8), 124 (61),123 (20), 122 (21),121
(17), 108 (6), 107 (8)
StL: Ropalospora viridis (T0nsb.) T0nsb.
TLC: A: 48, B': 79, C: 52 HoMoH 3' 4' 5'
HPLC: RJ 55 OH
Lit: C.F. Culberson et al. 1984; Elix and Wardlaw
Powder (MeOH), mp > 300 DC (coloration from
1987
220 DC)
React: N aOCI red
Isohyperplanaic acid (Isohyperplanasaure) UV (EtOH): 211 (4.56),269 (4.21), 303nm (3.99)
IH-NMR (90MHz,CDCl3 -CD 3 0D): 2.57 (6H,s,
CZ9H4007 (500.61)
Me-8,Me-8'), 6.21, 6.28, 6.60, 6.67 (4xlH,4xd,
J=3Hz,H-3,H-5,H-3',H-5')
7 11 I3C-NMR (l5.04MHz,DMSO-d6 ): C-l: 107.6, C-
Me-
2: 160.7, C-3: 100.6, C-4: 161.4, C-5: 110.1, C-6:
140.3, C-7: 167.6, C-8: 21.7, C-1': 116.3, C-2':
151.1, C-3': 107.1, C-4': 165.6, C-5', 112.5, C-6':
142.2 C-7': 171.8, C-8': 23.0
Deriv: Methyl tri-O-methylisolecanorate,
1 CO-O needles, mp 154-155 DC
StL: Parmotrema tinctorum (Nyl.) Hale
OMe- Lit: Sakurai and Goto 1987
3
Isomerochlorophaeic acid
Me- (Isomerochlorophaesaure)
5 IJ '
CZ4H300S (446.48)
Crystals (cyclohexane-EtOAc), mp 122-123 DC
IH-NMR (CDCI3 ): 0.86, 0.89 (2x3H,2xbt,J=
6.9Hz,Me-7",Me-5 111 ), 1.20-1.66 (l6H,m,-CH z-
2"-6",-CH z-2 111 -4111 ), 2.70 (2H,t,J=7.9Hz,-CH z-
OH
1"), 2.81 (2H,t,J=7.9Hz,-CH 2 -1 111 ), 3.85, 2.87,
3.93 (3x3H,3xs,3x-OMe), 6.37, 6.04 (2xlH, CO-O COOH
2xd,J:=2.2Hz,H-3,H-5), 6.74, 6.78 (2xlH,2xd,J=
2.2Hz,H-3',H-5') , Me-O
3 5'
MS, m/z 264 (17%), 163 (100) Me-
3
StL: Lecanora planaica Lumbsch
III
TLC: RF A: 0.55, B: 0.41, C: 0.58 Crystals (EtOAc), mp 146 DC

HPLC: RJ 0.51 IH-NMR (CDCI 3 ): 0.92, 0.98 (2x3H,2xt,J=7.2Hz,
Lit: Elix et al. 1994b Me-5",Me-3 111 ), 1.32-1.40, 1.50-1.80 (8H,m,4x-
CH z-), 2.79, 2.91 (2x2H,2xt,J=7.9Hz,7.7Hz,
-CHz-l",-CH z-l"'), 3.86, 3.96 (2x3H,2xs,2x-
Isolecanoric acid (Isolecanorsaure)
OMe), 6.47 (lH,s,H-5'), 6.42, 6.48 (2xlH,2xd,
Cl6Hl407 (318.27) J=2.1Hz,H-3,H-5)
3.16 Depsides 263
MS, mlz 235 (100%), 196 (2) 191 (2), 179 (2), 177 Needles (CHzClz-n-hexane), mp 146-147C
(2), 165 (2), 151 (4), 139 (3), 135 (3) IH-NMR (CDCl3): 0.86 (3H,t,J=6.5Hz,Me-9"),
StL: Ramalina sp. from Piji 1.20-1.28 (1 OH,m,-CH2-5"-8"), 1.54 (2H,bt,-
TLC: RF A: 0.49, B: 0.56, C: 0.54 CH z-4"), 2.44 (2H,t,J=7Hz,-CH z-3"), 2.64 (3H,
Lit: Elix et al. 1993a s,-Me), 3.86 (3H,s,-OMe), 4.08 (2H,s,-CH z-1"),
6.32, 6.48 (2X1H,2xd,J=2.6Hz,H-3',H-5'), 6.53,
6.65 (2x1H,2xd,J=2.2Hz,H-3,H-5), 11.29 (lH,
Isonorobtusatic acid (Isonorobtusatsaure)
bs,-OH)
C 17H 16 0 7 (332.30) MS, m/z 290 (15%),206 (18),191 (5), 177 (9),165
(9), 164 (79), 150 (25), 121 (21), 57 (100)
lc-O~OH
Wedin
TLC: RF A: 0.38, B: 0.33, C: 0.42
HO OH ~eOOH HPLC: Rj 0.44
Me Lit: Elix et al. 1994f
Microcrystals (acetone-cyc1ohexane), mp 168-
169C Isopseudocyphellarin A
React: NaOCl red
C21 H 22 0 S (402.39)
lH-NMR (acetone-d6 ): 2.00, 2.58 (9H,2xs,3x-
Me), 6.41, 6.51 (2H,2xd, J=2.5Hz,H-3,H-5), 6.80
10 8'
(lH,s,H-5')
MS, m/z 332 (M+,4%), 182 (58), 168 (32), 165
(18), 164 (90), 163 (8), 151 (69), 150 (70), 138
OH~*Me c o _ o * M e OH
(28), 137 (22), 136 (100), 135 (11), 124 (18), 123 g' 7'
HO OH Me eOOMe
(19), 122 (26)
StL: Ramalina americana Hale Me ME'
8 10'
TLC: RF A: 0.30, B: 0.53, C: 0.28
Lit: c.P. Culberson et al. 1990a; Elix et al. 1993a Prisms (CH 2Clz-n-pentane), mp 201C (dec.)
React: N aOCl red
Isopatagonic acid (Isopatagonsaure) IH-NMR (200MHz,CDCU: 2.07, 2.09, 2.13, 2.48,
2.99 (5x3H,5xs,5xMe-), 3.98 (3H,s,-COOMe);
CZSH300S (458.49) 10.37 (1H,s,CHO-9), 11.12, 12.17, 13.23 (3x1H,
g/l 3xs,3xHO-)
Mt> MS, m/z 402 (M+,5%), 210 (28), 194 (26), 193
(100),192 (8), 191 (6),179 (19), 178 (48), 164 (7),
150 (32), 149 (8), 121 (5),109 (6), 107 (8)
StL: Pseudocyphellaria pickeringii (Tuck.) D.
Gall.
TLC: A,: 73, B': 65, C: 78, E: 54
, Lit: Elix et al. 1987h
1 eO-O~3l' OH
OH 5' eOOH Isosphaeric acid (Isosphaersaure)
3
Me C23H2S07 (416.45)
7" IR (KBr): 69S, 73S, 78S, 808, 838, 88S, 980, 1000,
Me 1030, lOS0, 1080, llSO, ll7S, 1210, 12S0, 1290,
1320, 141S, 1464, lS00, 161S, 1640, 16S0, 3100,
3SS0, 36S0 cm- 1
IH-NMR (270MHz,acetone-d6): 2.51 (3H,s,Me-
8), 2.6S (3H,s,Me-8'), 6.31 (1H,d,J=2.4SHz,H-
co-o
OH
3' OH
3), 6.40 (1H,d,J=2.44Hz,H-3'), 6.72 (1H,d,J=
3
~COOH 2.4SHz,H-S), 6.76 (1H,d,J=2.44Hz,H-S')
13C-NMR (22.ll MHz,DMSO-d6 ): C-1: lOS.S, C-
Me 2: 162.2, C-3: 100.8, C-4: 162.7, C-S: ll1.8, C-6:
Needles (cyclohexane), mp 142C 141.6, C-7: 167.9, C-8: 22.S, C-1': ll6.2, C-2':
IH-NMR (200MHz,CDCl3 -acetone-d6): 0.77- 1S1.9, C-3': ll1.0, C-4': lS9.9, C-S': ll6.9, C-6':
1.03 (3H,m,Me-7"), 1.03-1.67 (10H,m,Sx- l37.9, C-7': 171.2, C-8': 21.S
CH 2-), 2.69 (3H,s,Me-8'), 3.00 (2H,bt,-CH 2-1"), MS, m/z 274 (3%), 168 (SO), ISO (100), 122 (3S),
3.90 (3H,s,OMe-4), 6.46 (2H,s,H-3,H-S), 6.68, 94 (IS); MS, m/z 318 (M-,lO%), 317 (20),300 (S),
6.80 (2x1H,2xd,J=2.SHz,H-3',H-S'), 11.20 (bs,- 273 (8), 167 (100), ISO (S8), 122 (78)
HO,-COOH) Deriv: Triacetyllecanoric acid, prisms, MeOH,
MS, m/z 267 (2.S%), 266 (1S), 249 (7), 248 (18), mp 190-191 c, from lecanoric acid with Ac2 0-
222 (19),207 (30),192 (ll), 191 (6),182 (28), 178 H 2S0 4
(S), 177 (ll), 169 (S), 168 (S2), 164 (29), lSI (26), StL: Hypocenomyce scalaris (Ach. ex Lilj.)
ISO (100), l39 (9),138 (92),137 (17), 13S (6), 12S M.Choisy, Parmotrema tinctorum (Nyl.) Hale
(6), 124 (47), 123 (28), 122 (43), 121 (8), 109 (6), TLC: A: 28, B: 44, B': 44, C: 22, G: S6
107 (7) HPLC: RJ 14
StL: Dimelaena oreina (Ach.) Norm., a MC: Pigs. 29B,C,D; 30A
chemotype from California Lit: c.P. Culberson 1969; Nicollier 1979
TLC: A: 43, B': 69, C: S3
Lit: c.P. Culberson et al. 1984, 1985; Elix and Loxodellic acid (Loxodellsaure)
Wardlaw 1987
C23 H 26 0 8 (430.44)
Lecanoric acid (Lecanorsaure) 1/

5
Me
Cl6Hl407 (318. 27)
8
HO#::-O~~~OH
CO-O 3' OH
MeO OH MCOOH
Me 3 ~
8'
Me
Needles (MeOH-H 2 0), mp 184C (dec.) 3'"
React: NaOCl red, PeCl3 violet
UV (EtOH): 214 (4.63), 270.5 (4.30), 30S.Snm Plates (MeOH), mp 137C
(4.09) React: KOH + NaOCl rose or red
3.16 Depsides 265
lR-NMR (CDCI3): 0.84 (3H,t,J=7.3Hz,Me-3 11f ), MS, m/z 240 (0.5%),224 (3), 222 (3),209 (2), 208
0.97 (3H,t,J=7Hz,Me-5"), 1.26-1.70 (4H,-CH2- (14),207 (100), 205 (1), 196 (2), 193 (1), 192 (2),
4",-CH 2-2 2.40 (2H,t,J=7.2Hz,-CH 2-3"), 2.97
11f
), 191 (5), 178 (2), 177 (2), 165 (1.5), 151 (1), 140
(2H,t,J=7.9Hz,-CH 2-1 11f ), 3.83 (3H,s,-OMe-4), (1), 139 (2), 135 (2), 92 (1),84 (1), 78 (5), 77 (2),
4.05 (2H,s,-CH 2-1") 6.29, 6.45 (2xlH,2xd,J= 56 (2), 52 (1), 51 (1),44 (5),41 (1)
2.5Hz,H-3,H-5), 6.50, 6.63 (2xlH,2xd,J=2.4Hz, Deriv: Methyl di-O-methylmerochlorophaeate,
H-3',H-5') plates (MeOH-H 2 0), mp 76-78C, from
MS, m/z 252 (3%),235 (14),234 (100), 191 (29), merochlorophaeic acid with an excess of CH1N1
178 (21), 177 (31), 164 (74), 152 (18), 137 (13) in Et20 for 5 days
135 (45), 124 (48),123 (22), 121 (12),77 (11), 71 StL: Cladonia merochlorophaea Asah.
(24),69 (16) TLC: A: 52, B: 56, B': 50, C: 53
StL: Neofuscelia loxodella (Ess1.) Ess1. HPLC: RJ 26
TLC: A: 39, B: 42, B': 42, C: 38 MC: Fig. 30B,C
HPLC: RJ 22 Lit: C.F. Culberson 1969; Elix and Norfolk 1975a
Lit: C.F. Culberson and Esslinger 1976; Elix and
Whitton 1989
2-0-Methylanziaic acid, Dihydropicrolichenic
acid (2-0-Methylanziasaure,
Merochlorophaeic acid Dihydropicrolicheninsaure)
(Merochlorophaesaure)
C2sH3107 (444.51)
C24H300S (446.48)
5"
311 Me
~1"
,:((CO-O
OH
OH
MeO 5 3 OMe HO
COOH
Me
Plates (MeOH-H10), mp 164-166C; needles 5 111
(benzene-cyclohexane) mp 160C
React: NaOCI purple to red" FeCl3 (EtOH) violet Needles (benzene-cyclohexane), mp 116-11rC
UV (EtOH): 220 (4.6), 259 (4.2), 295nm (3.8) IH-NMR (CDCI3): 0.84-0.96 (6H,m,Me-5",
IR (KBr): 1600, 1620, 1650, 1750, 1765, Me-5 11f
1.24-1.76 (12H,m,6x-CH 2-), 2.68,
),
3400cm-1 3.00 (2X2H,2xbt,J=7Hz,-CH 2-1",-CH 2-1 11f ), 3.83

IH-NMR (CDCI3): 0.87-1.11 (6H,m,Me-3",Me- (3H,s,2-0Me), 6.31 (2H,s,H-3,H-5), 6.67, 6.80
511f
1.27-1.91 (8H,m,4x-CH1-), 2.77, 2.89
), (2xlH,d,J=2Hz,H-3',H-5'), 7.00 (2H,bs,HO-,
(2X2H,2xbt,-CH 2-1",-CH2-1 11f ), 3.85, 3.96 -COOH), 11.20 (1H,bs,-OH)
(2x3H,2xs,2x-OMe), 6.45, 6.50 (2xlH,d, J= MS, m/z 238 (35%),224 (28), 222 (10),221 (61),
3Hz,H-3,H-5), 6.51 (1H,s,H-5'), 7.53, 9.80, 206 (51), 194 (17), 182 (86), 181 (19), 180 (21)
11.68 (3xIH,3xbs,2x-OH,-COOH) 178 (24), 177 (52), 168 (37), 167" (11), 164 (16),
163 (20), 151 (20), 150 (68), 149 (11),138 (100), 2' -O-Methylatranorin
137 (39), 135 (11), 124 (79), 123 (41), 122 (26),
121 (29) C2oHzoOs (388. 36)
StL: Ramalina americana Hale
TLC: A: 44, B': 38, C: 33
Lit: Davidson and Scott 1961; Elix 1974; C.F. ~CO-O~OMo
Culberson et aL 1990a
HO~OH ~COOMe
CHO Me
2'-O-Methylanziaic acid
(2'-0-Methylanziasaure) Plates (acetone), mp 146-148C
C2sH3207 (444.51) React: KOH yellow, PD yellow
IR (Nujol): 1075, 1110, 1190, 1250, 1280, 1650,
5/1 1660, 1750cm-1
Me
MS, m/z 388 (M+,2%), 210 (29), 180 (11), 179
(100),178 (30),177 (7),164 (5),163 (9), 150 (14),
149 (10)
CO-O OMe StL: Oropogon loxensis (Pee) Th.Pr.
TLC: A: 73, B: 53, B': 51, C: 72, E: 43
HO OH COOH Lit: C.P. Culberson and W.L. Culberson 1978;
3
Elix et aL 1989a
Methyl barbatate (Barbatinsauremethylester)

Me
5/11 Clo H 22 0 7 (374.38)
Plates (toluene-cyclohexane), mp 127-129C
~CO-O~OH
React: NaOCI red
1H -NMR (60 MHz,CDCI 3 -acetone-d6 ): 0.81-0.99
(6H,m,Me-5/1,Me-5"'), 1.23-1.83 (12H,m,6x-

CH 2-), 2.75, 2.99 (2x2H,2xbt,J=7.5Hz,-CH 2- MeO~OH ~COOMe
l/1,-CH 1 -1"'), 3.87 (3H,s,2'-OMe), 6.39 (2H,s, Me Me
H-3,H-5), 6.71 (2H,s,H-3',H-5'), 11.34 (bs,-
OH) Needles (MeOH), mp 173C
MS, m/z 239 (16%),238 (100),224 (40), 221 (21), MS, m/z 374 (M+), 196, 179, 178
207 (39), 206 (50), 195 (12), 194 (24), 182 (94), StL: Haematomma ochrophaeum (Tuck.) Mass.
181 (20), 178 (18),177 (48), 168 (16), 164 (9), 150 TLC: A: 77, B': 73, C: 86, E: 61
(21),138 (62), 137 (16), 124 (12) HPLC: R[ 47
Deriv: Methyl tri-O-methylanziate, needles Lit: c.P. Culberson et aL 1986
(MeOH), mp 57C, from 2'-0-methylanziaic
acid with MeJ-K 1C0 3
Methyl 5-chloro-4-0-demethylbarbatate
StL: Lecidea diducens NyL, L.speirodes NyL
(5-Chlor-4-0-demethylbarbatin -
TLC: A: 46, B: 40, B': 42, C: 34
sauremethylester)
HPLC: R[ 29
Lit: c.P. Culberson and Hertel 1972; Elix 1974 C19H19CI07 (394.79)
3.16 Depsides 267
2-0-Methylconfluentic acid
CI*Meco_o*Me OH (2-0-Methylconfiuentinsaure)
HO OH 5 COOMe C29H3S0S (514.59)
Me Me 1]"
Me
Crystals (CHCI3), mp 162-164, 165-166 DC
React: NaOC1 red
IH-NMR (CDCI3): 2.01, 2.12, 2.47, 2.70 (4x3H,
4xs,4x-Me), 3.93 (3H,s,-COOMe), 6.23 (lH,s,
HO-4), 6.45 (lH,s,H-5'), 11.65, 12.11 (2x1H, OMe
2xs,HO-2,HO-2')
MS, m/z 394 (M+,4%), 201 (34), 199 (l00), 198 COOH
(5), 196 (5), 165 (7), 164 (13), 136 (12)
StL: Erioderma sp.
TLC: A: 81, B: 81, C: 76
Lit: Elix et al. 1987g Me
5"(
Methyl 5-chloronorobtusate Needles (MeOH-H 20), mp 135-136 DC

(5-Chlornorobtusatsauremethylester) UV (MeOH): 208 (4.55), 260 (3.86), 284nm
(3.75)
ClsHl7CI07 (380.77) IR (KBr): 660, 795, 825, 840, 900, 950,1038,1080,
1100, 1140, 1150, 1205, 1220, 1255, 1290, 1320,
Me 1345, 1422, 1462, 1585, 1690, 1725, 1750, 2940,
CI*CO-O 3' OH 3100,3450cm-1
HO OH ~COOM' IH-NMR (60 MHz, C6D6): 0.86 (6H,t,Me-7",Me-

5111 ) , 1.00-1.90 (l2H,m,6x-CH 2-), 2.35 (2H,t,
Me Me -CH z-3"), 2.80 (2H,t,-CH z-l lII ) , 3.32, 3.40, 3.44
(3x3H,3xs,3x-OMe), 2.85 (2H,s,-CH 2-1"), 6.38,
Needles (CH 2CI 2-n-pentane), mp 164 DC 6.44, 6.89, 7.08 (4x1H,4xd,J=2Hz,H-3,H-5,
React: NaOCI red H-3',H-5')
IH-NMR (CDCI3): 2.19, 2.58, 2.72 (3x3H,3xs, MS, m/z 514 (M+), 443, 415, 368, 315, 277, 276,'
3xMe-), 3.99 (3H,s,-COOMe), 6.28 (lH,s,HO- 257,238,220, 205, 191, 182, 178, 177, 150, 149,
4), 6.60, 6.74 (2H,2xs,H-3',H-5'), 11.30, 11.60 138,123, 106,71,69,57,44,41 (100%)
(2X1H,2xs,HO-2,HO-2') Deriv: Methyl 2-0-methylconfiuentate, needles
MS, m/z 380 (M+,0.2%), 201' (17),200 (10), 199 (MeOH-HzO), mp 81-82 DC, from 2-0-meth-
(54), 198 (17), 182 (38), 170 (11), 151 (31), 150 ylconfiuentic acid with excessive CHzN z in EtzO
(100),142 (5), 122 (48), 121 (7), 107 (9) in 12h at 20 DC
StL: Erioderma sp. StL: Lecidea fuscoatra (L.) Ach.
TLC: RF A: 0.68, B: 0.68, C: 0.72 TLC: A: 43, B': 25, C: 44
Lit: Elix et al. 1989a HPLC: R] 28
MC: Fig. 62B,C
Lit: Huneck and Schreiber 1974; Elix and
Ferguson 1977, 1978
5//
4-0-Methylcryptochlorophaeic acid .
(4-0-Methylcryptochlorophaesaure) Me
CZ6H340S (474.53)
OH
5'/
Me
OMe MeO
3
OH
CO--O
Me
5/11
MeO OMe HO
3
Needles (CHCI3-CCI4), mp 152C
IH-NMR (CDCI3-acetone-d6): 0.90 (6H,bt,Me-
Me 5",Me-5 111 ) , 1.09-2.00 (6H,m,3x-CH z-), 2.66-
5'" 3.20 (4H,m,-CH z-1",-CH z-1 111 ), 3.89, 3.98 (2x
Needles (benzene-n-hexane), mp 141-142C 3H,2xs,2x-OMe), 6.48 (2H,s,H-3,H-5), 6.50
React: N aOCI red (1H,s.H-5'), 6.86 (bs,HO-,-COOH)
UV (EtOH): 216, 259, S 292nm MS, miz 254 (1%), 238 (l3), 236 (7),221 (8),210
IR (Nujol): 1035, 1165, 1215, 1265, 1580, 1620, (23), 195 (5), 194 (11), 182 (31), 181 (8), 177
1650, 1750, 2500-2800, 3350cm-1 (19), 167 (10), 164 (5), 154 (41), 153 (74), 152
IH-NMR (60MHz,CDCI3): 0.92 (6H,bt,Me-5", (9), 151 (12), l39 (14), l38 (100), l37 (21), 123
Me-Sill), 1.32-1.84 (12H,m,6x-CH z-), 2.72- (8)
3.03 (4H,m,-CH z-1",-CHz-1 111 ), 3.82, 3.94 StL: Ramalina asahinae W.Culb. et C.Culb.
(2x3H,2xs,2x-OMe), 6.43, 6.48 (2x1H,2xd,H- TLC: A: 32, B': 18, C: 27
3,H-5), 6.49 (1H,s,H-5'), 7.36, 10.41, 11.71 HPLC: R, 26
(3H,3xbs,2xHO-,-COOH) Lit: Elix and Wardlaw 1986
MS, miz 252 (8%), 240 (4),236 (17), 235 (100),
222 (18), 196 (17), 191 (7), 179 (5), 165 (7), 152 Methyl 4-0-demethylbarbatate
(6), 151 (6), 140 (4), l39 (8), l37 (7), 120 (5),91 (4-0-Demethylbarbatinsauremethylester)
(9),79 (6),78 (6),77 (11), 69 (7), 67 (5), 65 (8),
63 (5), 55 (7), 53 (9), 51 (7), 44 (55), 43 (8), 41 Cl9H2007 (360.35)
(25)
Me Me
StL: Cladonia perlomera Krist.
TLC: A: 60, B: 61, B': 56, C: 66 ~CO-O~OH
HPLC: R, 32
Lit: c.P. Culberson and Kristinsson 1969; Elix
HO~OH ~COOMe
and Norfolk 1975a; Shibuya et al. 1983 Me Me
Needles (MeOH), mp 108-111 c

4'-0-Methylcryptochlorophaeic acid React: N aOCI red
(4' -0-Methylcryptochlorophaesaure) IH-NMR (60MHz,CDCI3): 2.10, 2.14, 2.50, 2.60
(4x3H,4xs,4x-Me)
CZ6H340S (474.53) StL: Oropogon loxensis (Pee) Th.Pr.
TLC: A: 59, B: 57, B': 59, C: 47, E: 43
3.16 Depsides 269
HPLC: Rj 31 MethyI2,2'-di-O-methyleriodermate
Lir: c.P. Culberson and W.L. Culberson 1978 (2,2,' -Di -O-methyleriodermsauremethylester)
C22 H zs CI0 7 (436.87)
Methyl 3,5-dichlorolecanorate, Tumidulin
(3,5-Dichlorlecanorsauremethylester)
CI*Mec o _ o * M e OMe
Cl7Hl4Cl207 (401.19)
*
8 HO OMe Me COOMe
Me
7 I Me Me
CI 6 1 CO-O ft' 3 2' OH
HO 4
5
3
2
OH
Yrr:7'
5~COOMe
Needles (CHzClz-n-pentane), mp 168C
lH-NMR (CDCI3 ): 2.20, 2.27, 2.48 (15H,3xs,
Cl Me 5x-Me), 3.78, 3.82 (2x3H,2xs,2x-OMe), 3.92
8' (3H,s,-COOMe), 5.98 (lH,s,HO-)
Needles (MeOH-H 20), mp 177-177.5 c MS, m/z 436 (M+,0.050/0), 215 (32), 214 (11), 213
React: NaOCI red (100), 193 (12), 170 (5),91 (5)
UV (EtOH): 259 (4.20), 318nm (4.10) StL: Erioderma sp.
IR (KBr): 700, 740, 770, 790, 810, 850, 878, 955, TLC: A: 63, B': 47, C: 58, E: 35
980, 1005, 1040, 1062, 1090, 1105, 1140, 1185, HPLC: Rj 25
1210, 1235, 1260, 1300, 1330, 1380, 1420, 1450, Lit: Elix et aI. 1987g
1500, 1570, 1590, 1610, 1640, 1670, 3000, 3180,
3500cm-1
2-0-Methyldivaricatic acid
lH-NMR (60MHz,CDCI3): s 2.73, 2.97 (2x3H,
(2-0-Methyldivaricatsaure)
2xs,Me-8,Me-8'), 4.32 (3H,s,-COOMe), 7.12,
7.25 (2X1H,2xd,H-3',H-5') CZZHZ607 (402.43)
13C-NMR (25.05MHz,DMSO-d6): C-1: 110.2, C-
Me
2: 150.7, C-3: 108.6, C-4: 151.4, C-5: 114.1, C-6:
132.8, C-7: 164.8, C-8: 17.5, C-1': 118.3, C-
2': 156.3, C-3': 106.8, C-4': 151.4, C-5': 113.7, C- CO-O OH
6': 138.0, C-7': 167.6, C-8': 19.6, C-1-COOMe:
51.7
MS, m/z 404 (M+,50/0), 402 (25),400 (36), 372 (3),
370 (10),368 (14),333 (10),221,219, 182, 151,
Me
150,120,94
Deriv: Methyl tri-0-methyl-3,5-dichloroleca- Needles (cyclohexane), mp 118C
norate, prisms (MeOH), mp 148-149C, from lH-NMR (CDCI 3): 1.00 (6H,bt,J=7.0Hz,2x-CHz-
methyl 3,5-dichlorolecanorate with CH 2N2 at Me), 1.40-2.50 (4H,m,2x-CH z-Me), 2.57-3.22
20C in 24h (4H,m,2xbenzyl.-CH2-), 3.88, 3.91 (2x3H,2xs,
StL: Ramalina tumidula (Tayl.) Hun. et Pollm. 2xMeO-), 6.43 (2H,s,H-3,H-5), 6.70, 6.88 (2H,
TLC: A: 67, B: 62, B': 57, C: 58, E: 21 2xd,J=2.5Hz,H-3',H-5'), 10.50 (2H,bs,-COOH,
HPLC: Rj 24 HO-)
MC: Pig. 36A,B MS, m/z 302 (0.6%), 224 (9), 208 (13),207 (100),
Lit: Huneck 1966a; c.P. Culberson 1969; 196 (10), 191 (13),178 (20), 152 (10), 150 (6), 137
Sundholm and Huneck 1980 (5), 124 (15), 123 (9), 121 (7)
StL: Ramalina sayreana W.Culh. et C.Culb. Prisms (CHzClz-n-pentane), mp 165C

TLC: A: 46, B: 52, B': 52, C: 46 React: N aOCI red
HPLC: Rr 28 IH-NMR (CDCI 3): 2.08 (6H,s,2xMe-), 2.20, 2048,
Lit: W.1. Culberson and C.P. Culberson 1981; 2.80 (3x3H,3xs,3xMe-), 3.98 (3H,s,-COOMe),
Elix et al. 1985c 6.30, 11.21, 11.83 (3xIH,3xs,3xHO-)
MS, m/z 408 (M+,2%), 210 (29), 201 (32), 200
(15), 199 (100), 198 (15), 179 (23), 178 (67), 170
2' -0-Methyldivaricatic acid
(9), 151 (7), 150 (65), 149 (10), 107 (16)
(2'-0-Methyldivaricatsaure)
StL: Erioderma sp.
CZ2Hz607 (402043) TLC: A: 69, B': 71, C: 77, E: 57
3"
HPLC: Rr 39
Me Lit: Elix et al. 1987g
fl
3' Methyl evernate (Evernsauremethylester)
1 CO-O OMe
ClsHlS07 (346.32)
Me ~CO-O~OH
3 111
Prisms (cyclohexane), mp 142-143C MeO~OH ~COOMe

IH-NMR (CDCI3 ): 0.97, 0.98 (2x3H,2xt,J=7.3Hz, Me
Me-3",Me-3"'), 1.70 (4H,m,-CH z-2",-CHz-2"'), Crystals (MeOH), mp 142-143C
2.76, 2.97 (2x2H,2xt,J=7.7,7.8Hz,-CH 2-1",- IR (KBr): 1620, 1658cm-1
CH z-l l11 ) , 3.85, 3.91 (2x3H,2xs,2x-OMe), 6.39 IH-NMR (DMSO-d6): 2.25, 2.39 (2x3H,2xs,
(2H,d,J=2.3Hz,H-3',H-5'), 6.70 (2H,d,J=2.3Hz, 2xMe-), 3.76 (2H,s,MeO-), 3.82 (3H,s,-
H-3,H-5), llAI (1H,s,HO-) COOMe), 6.37, 6.60 (2X2H,H-3,H-5,H-3',H-
MS, m/z 210 (28%), 194 (12),193 (100), 192 (25), 5'), 10.27 (2H,bs,2xHO-).
177 (64), 164 (14), 135 (33) MS, m/z 346 (M+), 182, 165 (100%), 150, 122
StL: Pertusaria velloziae (Vain.) Archer et StL: Peltigera aphthosa (1.) Willd.
Elix TLC: A: 71, B': 64, C: 76, E: 52
TLC:A:45, B:48,C: 50 HPLC: Rr 16
HPLC: R] 28 Lit: Maass 1975a
3'-Methylevernic acid (3'-Methylevernsaure)

Methyl eriodermate
(Eriodermsauremethylester) C1s H 1s0 7 (346.32)
C2o H 21 CI 0 7 (408.82) 8 8'
Me Me
CI*Me co_o*Me OH ~
5
1 to-o
2
4'
,
3' 2'
f 7'
OH
Mea 4 3 OH 5 6' COOH

HO OH Me COOMe
Me
Me Me 9'
3.16 Depsides 271
Crystals (n-hexane), mp 159C !3C-NMR (22.11 MHz,DMSO-d 6 ): C-1: 109.9, C-

Uv (MeOH): 230, 267-270, 305nm 2: 160.2, C-3: 99.2, C-4: 162.6, C-5: 109.9, C-6:
IR (KBr): 1090, 1150, 1210, 1235, 1440, 1500, 140.4, C-7: 167.3, C-8: 18.7, C-4-0Me: 56.1, C-
1570, 1620, 1650,2930-2960,3060, 3400 cm- 1 I': 123.1, C-2': 151.3, C-3': 103.5, C-4': 156.7, C-
IH-NMR (60MHz,DMSO-d6 ): 2.05 (3H,s,Me-8'), 5': 108.6, C-6': 136.1, C-7': 168.2, C-8': 21.3,
2.40 (6H,s,Me-8,Me-9'), 3.75 (3H,s,MeO-4), C-2'-OMe: 55.2
4.60 (1H,s,HO-), 6.35 (2H,s,H-3,H-5), 6.50 MS, m/z 302 (3%),182 (12), 166 (9), 165 (78), 164
(1H,s,H-5'), 10.40 (1H,s,HO-) (26), 139 (8), 138 (100), 137 (12), 136 (17), 124
13C-NMR (22.11 MHz,DMSO-d 6 ): C-1: 108.0, C- (15),109 (50), 108 (30), 107 (48), 95 (20),94 (12),
2: 162.1, C-3: 99.0, C-4: 162.9, C-5: 110.3, C-6: 93 (26),79 (20), 78 (12), 77 (26), 65 (20),44 (73),
140.9, C-7: 167.4, C-8: 22.3, C-4-0Me: 55.2, C- 39 (52)
I': 115.9, C-2': 152.1, C-3': 109.2, C-4': 161.7, C- StL: Evernia prunastri (L.) Ach.
5': 115.9, C-6': 139.4, C-7': 173.5, C-8': 9.11, TLC: A: 38, B': 33, C: 43
C-9': 23.30 Lit: Nicollier et al. 1979a
MS, m/z 346 (M+,63%), 183 (6), 182 (37), 167
(11), 166 (46), 165 (100), 164 (68), 150 (6), 149
2-0-Methylglomelliferic acid
(17), 138 (12), 137 (11), 136 (54), 122 (6), 121
(2-0-Methylglomellifersaure)
(11),108 (11), 107 (11), 95 (12),79 (11), 77 (14),
69 (6),67 (6),44 (11),43 (23) C26H 32 0 S (472.52)
StL: Evernia prunastri (L.) Ach.
TLC: A: 43, B': 62, C: 49 Me
HPLC: Rr 32
Lit: Nicollier et al. 1979a
co-O OH
2'-0-Methylevernic acid
(2' -0-Methylevernsaure) MeO COOH
ClsHlS07 (346.32)
tt
8 Me
Me 7 '
5 6 1 CO-O 4,3 2' OMe Physical data not yet known
2 l' , StL: Chemotype of Ramalina americana Hale
MeO 4 3 OH tOOH TLC: A: 42, B': 42, C: 52
Me Lit: c.P. Culberson et al. 1990a; Elix and Ernst-
8' Russell 1993
Crystals (EtOAc-n-pentane), mp 162C

Methyl 8-hydroxybarbatate
UV (MeOH): 230, 267-270, 300nm
(8-Hydroxybarbatinsauremethylester)
IR (KBr): 1210, 1255, 1260, 1435, 1500, 1620,
1675, 2930-2970, 3060, 3400 cm- 1 C22 H 22 0 S (414.40)
IH-NMR (60MHz,DMSO-d6 ): 2.22, 2.40 (2x3H,
2xs,2xMe-), 3.75 (6H,s,2xMeO-), 6.35, 6.75
(2X2H,2xs,H-3,H-5,H-3',H-5'), 10.45 (1H,s,
-OH)
StL: Oropogon loxensis (Fee) Th.Fr.
MeO*::-O*::OM.
TLC:A:46,B:36,C:35
Lit: C.F. Culberson and W.L. Culberson 1978;
Elix et al. 1993a
CH 20H Me
8
2-0-Methylhyperlatolic acid
Crystals (CHzClz-n-pentane), mp 148-152C (2-0-Methylhyperlatolsaure)
(sublimation)
CZSH3S07 (486.58)
IH-NMR (CDCl3 ): 2.07, 2.53, 2.69 (3x3H,3xs,
3xMe-), 3.91, 3.97 (2x3H,2xs,2x-OMe), 4.78
5"
(2H,s,-CH z-8), 6.40, 6.51 (2x1H,2xs,H-5,H-5'), Me
11.71, 11.94 (2x1H,2xs,2x-HO-)
MS, mlz 372 (5%), 196 (32), 195 (7),155 (56), 164
(81),136 (100)
StL: Erioderma sp.
TLC: RF A: 0.63, B: 0.38, C: 0.47
Lit: Elix et al. 1993a MeO
3
Methyl 8-hydroxy-4-0-demethylbarbatate
(8-Hydroxy-4-0-
demethylbarbatinsauremethylester)
Me
Cl9H200S (376.35) 7'"
HO~::-O~::OM'
Crystals (n-pentane - cyclohexane), mp 82-
83C
IH-NMR (CDClJ: 0.89, 0.90 (2x3H,2xt,J=6.9Hz,
Me-5",Me-7"'), 1.35, 1.55 (16H,2xm,-CH z-2"-
CH20H Me 4",CH z-2"'-6"'), 2.69, 2.98 (2x2H,2xm,-CH 2-
8
1",-CH2-1"'), 3.85, 3.87 (2x3H,2xs,2x-OMe),
Needles (CHzClz-n-pentane), mp 156C (subli- 6.39 (2H,d,J=2.3Hz,H-3',H-5'), 6.72 (2H,d,J=
mation); crystals (acetone), softens above 2.3Hz,H-3,H-5), 11.46 (1H,sHO-)
135C, amorphous at 148-158C, and melting MS, m/z 236 (15),235 (100), 124 (31)
slowly up to 190C (dec., sublimation) StL: Pertusaria follmanniana A.W. Archer et
React: NaOCl red Elix, Pertusaria modesta MUll.-Arg.
IR (Nujol): 1150, 1265, 1300, 1535, 1565, 1650, TLC: A: 44, B: 58, C: 52
3200-3600 cm- 1 HPLC: R[ 42
IH-NMR (CDClJ: 2.08, 2.53, 2.62 (3x3H,3xs,3x- Lit: Elix et al. 1995f
Me), 3.98 (3H,s,-COOMe), 5.08 (2H,s,-CH z-8),
6.37, 6.51 (2XIH,2xs,H-5,H-5'), 8.88, 11.78,
2' -0- Methylhyperlatolic acid
11.94 (3xIH,3xs,3x-OH)
(2' -0-Methylhyperlatolsaure)
MS, mlz 376, 234, 196, 164 (100%), 136, 196
(42%),164 (97), 136 (100) CZSH3S07 (486.58)
3.16 Depsides 273
TLC: B: 59, C: 60
Lit: C.P. Culberson et al. 1987
2' -O-Methylhyperphyllinic acid

(2' -0-Methylhyperphyllinsaure)
OH
C3zH 4P9 (570.66)
Physical data unknown, only microchemicaily

identified
MS, mlz 266, 183, 182 CO-O
StL: Pseudobaeomyces pachycarpa (Mull.Arg.)
Sato OH
TLC: A: 59, B': 62, C: 55
Lit: C.P. Culberson et al. 1987; Elix and Ernst-
Russell 1993
4-0-Methylhyperolivetoric acid or
(4-0-Methylhyperolivetorsaure)
C29H3S0S (514.59)
CO-O
OH
Physical data unknown, only microchemically

identified
Physical data unknown, only micro chemically StL: Pseudobaeomyces pachycarpa (Mull.Arg.)
identified Sato
StL: Pseudobaeomyces pachycarpa (Mull.Arg.) TLC: A: 46, B: 33, C: 41
Sato HPLC: R, 32
Lit: C.P. Culberson et al. 1987; Elix and Ernst- 5" 5"/
Russell 1993 Me Me
2'-0-Methylimbricaric acid
(2'-0-Methylimbricarsaure) eo-O eOOH
C24H 30 0 7 (430.48) OMe HO OH
3 5'
5"
Mt> Prisms (EtOAc-cyclohexane), mp 152-153 DC
IH-NMR (CDC13): 0.86, 0.90 (2x3H,2xt,]=6.6,
6.8Hz,Me-5",Me-5"'), 1.20-1.69 (12H,m,6x-
CH 2-), 2.71, 2.90 (2x2H,2xt,]=7.2,8.6Hz,-CH 2-
CO-O 3' OMe
I", CH2-1"'), 3.88, 3.98, (2x3H,2xs,2x-OMe),
6.44, 6.50 (2x1H,2xd,J=2.2Hz,H-3,H-5), 6.52
MeO OH ;'((COOH
(1H,s,H-5'), 8.02, 11.51 (2x1H,2xs,2x-OH)
3 ~ MS, m/z 252 (1%),251 (7), 236 (16),235 (100),
Mt> 191 (2), 178 (2), 151 (3)
3'" StL: Pertusaria paradoxica Archer et Elix
TLC: RF A: 0.43, B: 0.54, C: 0.48
Needles (CH 2CI2-n-pentane), mp 126 DC
IH-NMR (CDCIJ: 0.97 (6H,bt,Me-5",Me-3"'),
1.16-1.83 (8H,m,4x-CH 2-), 2.61-3.11 (4H,m,-
CH2-1",-CH 2-1"'), 3.83, 3.90 (2x3H,2xs,2x- 2-0-Methylisohyperlatolic acid
OMe), 6.38 (2H,s,H-3',H-5'), 6.67, 6.71 (2x1H, (2-0-Methylisohyperlatolsaure)
2xd,]=2Hz,H-3,H-5), 11.33 (lH,s,-OH)
MS, m/z 430 (M+,O.4%), 238 (19), 222 (21), 221 C28H3S07 (486.58)
(98), 220 (43), 211 (10), 210 (71), 195 (9), 194
(13), 193 (51), 192 (17), 191 (24), 182 (41), 181
(20),179 (5), 178 (24),177 (100), 175 (6), 167 (5),
166 (9),165 (19), 164 (65), 163 (25), 162 (5),151
(14),150 (6), 149 (12), 148 (5), 147 (6),138 (48),
137 (30), 136 (8), 135 (24)
StL: Lecidea cyanosarca Zahlbr. 3'
TLC: A: 46, B': 49, C: 59 eo-o OH
HPLC: RI 36 Mt>O COOH
Lit: c.P. Culberson et al. 1987; Elix et al. 1993a
i 3
4-0-Methylisocryptochlorophaeic acid
(4-0-Methylisocryptochlorophaesaure) Me
5'"
C26H340S (474.53)
Crystals (cyclohexane), m p 84 DC
IH-NMR (CDCI3): 0.87, 1.91 (2x3H,2xt,]=6.9,
7.0Hz,Me-7",Me-5"'), 1.26, 1.37, 1.64 (16H,3xm,
3.16 Depsides 275
-CH z-2"-6",-CH z-2/f/-4/f/), 2.69, 2.99 (~x2H, 2'-0-MethylisopseudocypheUarin A

2xm,-CH z-1",-CH z-l/f/), 3.84, 3.86 (2x3H,2xs,
C22 H 24 0 S (416.41)
2x-OMe), 6.38 (2H,d,J=2.3Hz,H-3',H-S'), 6.73
(2H,d,J=2.3Hz,H-3,H-S), 11.33 (1H,s,HO-) 8
MS, m/z 264 (16%),263 (100), 196 (37), 150 (22) Me Me
StL: Pertusaria follmanniana Archer et Elix,
Pertusaria modesta Miill.-Arg.
OH~*CO-O*OMe
TLC:A:44,B:63,C:60 HO OH Me 6 eOOMe
9
HPLC: Rj 45 Me Me
Lit: Elix et al. 1995f 8
Plates (CH 2Clz-n-pentane), mp 171C

2' -0-Methylisohyperlatolic acid React: NaOCI red, PD yellow
(2' -O-Methylisohyperlatolsaure) IH-NMR (200MHz,CDCI3): 2.07, 2.11, 2.13, 2.22,
2.99 (Sx3H,5xs,5xMe-), 3.78 (3H,s,-OMe), 3.95
C2sH3S07 (486.58) (3H,s,-COOMe), 10,37 (1H,s,CHO-9), 12.17,
13.23 (2x1H,2xs,2x-OH)
7"
Me MS, m/z 416 (M+,l %),224 (28),195 (6), 194 (38),
193 (100), 192 (22), 191 (8), 177 (7), 165 (5), 164
(9),163 (9), 150 (7), 149 (6), 135 (7), 134 (6),121
(5), 109 (8), 107 (7)
StL: Pseudocyphellaria pickeringii (Tuck.)
OMe
D.Gall.
TLC: A: 69, B': 49, C: 65, E: 40
OH eOOH Lit: Elix et al. 1987h
Methyllecanorate (Lecanorsauremethylester)
Me C17Hl607 (332.30)
5'"
Me
Crystals (EtOAc-cyclohexane), mp 127-128.S o C
IH-NMR (CDCI3 ): 0.84,0.89 (2x3H,2xbt,J=7Hz,
~eo-o OH
Me-7",Me-S/f/), 1.18-1.73 (16H,m,8x-CH1 - ) , HO OH VeOOM.
2.78, 2.97 (2x2H,2xt,J=7.9Hz,-CH z-1",-CH 2-
Me
1"'), 3.85, 3.9l (2x3H,2xs,2x-OMe), 6.39 (2H,
s,H-3',8:-S'), 6.67, 6.72 (2xlH,2xd,J=2.1Hz, Crystals (benzene), double mp 149 and 298C
H-3,H-S), 11.39 (s,-OH) (dec.)
MS, mlz 238 (32%),221 (10), 183 (10), 182 (100), React: NaOCI red
181 (24), 178 (14), 177 (75), 164 (25), 151 (16), IR (KBr): 1422, 1440, 1470, 1500, 1577, 1614,
138 (100), 137 (36), 135 (14), 123 (29) 1638, 1670, 3430 cm- l
StL: Biatora sorediosa Rambold IH-NMR (CDCI 3 ): 2.57, 2.62 (2x3H,2xs,2xMe-),
TLC: A: 51, B': 58, C: 63 3.98 (3H,s,-COOMe), 5.24 (s,-OH), 6.30 (2H,s,
HPLC: Rj 44 2xarom.-H), 6.95, 6.70 (2H,2xarom.-H), 11.20,
Lit: Elix and David 1991 11.47 (2H,2x-OH)
MS, m/z 332 (M+), 182, 150 (100%), 122 MS, m/z 422 (M+,l%), 215 (33), 214 (15), 213
StL: Pseudocyphellaria crocata (1.) Vain. (100),212 (l3), 211 (5), 210 (28), 184 (10), 179
TLC: A: 52, B': 48, C: 39, E: 30 (23),178 (62), ISO (67), 149 (14),141 (6), 122 (5),
Lit: Maass 1975b 121 (7),107 (11), 91 (11)
StL: Erioderma sp.
TLC: A: 77, B': 78, C: 87, E: 71
Methyl 2-0-methyleriodermate
Lit: Elix et al. 1987g
(2-0-Methyleriodermsauremethylester)
C21 H z3 CI0 7 (422.84)
Methyl 2'-0-methyleriodermate
(2' -0-Methyleriodermsauremethylester)
CI*Me co_o*Me OH C21H23CI07 (422.84)
HO OMe Me COOMe
CI*Me co_o*Me OMe
Me Me
Prisms (CH zCI2-n-pentane), mp 167C HO OH Me COOMe

IH-NMR (CDCI3): 2.20 (6H,s,2xMe-), 2.25(3H,s, Me Me
Me-), 2.48 (6H,s,2xMe-), 3.83 (3H,s,-OMe),
Prisms (CHzClz-n-pentane), mp 172 c
3.98 (3H,s,-COOMe), 5.98,11.20 (2x1H,2xs,2x-
IH-NMR (CDCI3): 2.07, 2.10 (2x3H,2xs,2xMe-),
OH).
2.22 (6H,s,2xMe-), 2.81 (3H,s,Me-), 3.80 (3H,s,-
MS, m/z 422 (M+,0.2%), 215 (32), 214 (12), 213
OMe), 3.97 (3H,s,-COOMe), 6.32,11.83 (2H,2xs,
(100), 178 (7), 170 (5), 150 (6)
2x-OH)
StL: Erioderma sp.
MS, m/z422 (M+,l%), 225 (6),224 (47), 201 (29),
TLC: A: 66, B': 61, C: 66, E: 46
200 (l3), 199 (87), 198 (12), 194 (12), 193 (100),
HPLC: Rr 31 192 (23), 178 (5), 177 (12), 170 (7), 163 (9), ISO
Lit: Elix et al. 1987g
(12), 149 (11), l35 (8), l34 (11), 121 (6), 107 (l3),
91 (l3)
MethyI4-0-methyleriodermate StL: Erioderma sp.
(4-0-Methyleriodermsauremethylester) TLC: A: 67, B': 58, C: 65, E: 47
HPLC: Rr 30
CZIHz3CI07 (422.84) Lit: Elix et al. 1987g
~:*::~:*::OM'
Methyl 3' -methyllecanorate
(3'-Methyllecanorsauremethylester)
ClsHlS07 (346.32)
b ' to-o
Me Me
8 8'
Amorphous solid (CHzClz-n-pentane), mp Me Me
124C
5 , 3' t OH
IH-NMR (CDCI3): 2.08 (6H,s,2xMe-), 2.21. 2.46,
4, " 7'
2.82 (3x3H,3xs,3xMe-), 3.88 (3H,s,MeO-), 3.91 HO 4 3 OH 5 6' COOMe
(3H,s,-COOMe), 5.98, 11.23 11.64 (3x1H,3xs, Me
3x-OH) 9'
3.16 Depsides 277
Crystals (cyclohexane), mp 125-128C Needles (EtOAc-n-pentane), mp 147-148C

React: NaOCl red, FeCl3 (EtOH) violet IH-NMR (CDCI3): 0.70-0.96 (6H,m,Me-7/1,Me-
UV (MeOH): 230, 267-271, 306nm 7111 ), 1.12-1.64 (6H,m,3x-CH 2 -), 2.30-2.59 (2H,
IR (KBr): 1100, 1150, 1190, 1250, BOO, 1390, m,-CH 2-3"), 3.62, 4.04 (2X2H,2xs,-CH 2-1/1,-
1445, 1580, 1625, 1660,2920-2970, 3420cm-1 CH 2-1 111 ), 3.83, 3.96 (2x3H,2xs,2x-OMe), 6.26,
IH-NMR (60 MHz,CDCI3): 2.20 (3H,s,Me-8'), 6.44, 6.60, 6.72 (4x1H,4xd,J=2Hz,H-3,H-5,H-
2.50 (3H,s,Me-9'), 2.60 (3H,s,Me-8), 3.95 3',H-5')
(3H,s,-COOMe), 6.35 (2H,s,H-3,H-5), 6.50 MS, m/z 262 (40%),236 (47),207 (10), 206 (30),
(1H,s,H-5'). 177 (12),164 (38), 138 (34), 137 (33),135 (17),99
I3C-NMR (22.11 MHz,DMSO-d6 ): C-1: 105.5, C- (100), 71 (74),43 (100)
2: 162.2, C-3: 100.8, C-4: 162.7, C-5: 111.8, C-6: StL: Paraporpidia leptocarpa (Bag. et Mitt.)
141.6, C-7: 167.9, C-8: 22.5, C-1': 116.2, C-2': Rambold et Hertel
152.0, C-3': 111.0, C-4': 160.0, C-5': 117.0, C-6': TLC: A: 41, B: 29, B': 19, C: 36
137.9, -COOMe: 52.1, C-8': 9.2, C-9': 22.8 HPLC: Rj 25
MS, m/z 346 (M+,16%), 197 (9),196 (74), 168 (2), Lit: Chester and Elix 1981b
166 (9), 165 (32),164 (98), 163 (19), 152 (32),151
(100), 150 (9), 137 (28), 136 (93), 135 (37), 121
2'-0-Methylnorbarbatic acid
(9),109 (14), 108 (23), 107 (37),91 (12),83 (19),
(2' -0-Methylnorbarbatinsa ure)
79 (46), 77 (45), 69 (28), 55 (32), 53 (45),43 (32)
StL: Evernia prunastri (1.) Ach. Cl9H2007 (360.35)
TLC: A: 55, B': 53, C: 40, E: 30
~co-o~o",
HPLC: RI27
LIt: Nicollier et al. 1979a
HO~OH ~COOH
2'-0-Methylmicrophyllinic acid
Me Me
(2'-0-Methylmicrophyllinsaure)
Rosettes (Et2 0-n-pentane), mp 162C
C30H3S09 (542.60) React: NaOCl red
IH-NMR (CDC13): 2.14 (6H,s,2xMe-), 2.47, 2.61
7" (2x3H,2xs,2xMe-), 3.88 (3H,s,MeO-), 6.31, 6.83
Me
(2X1H,2xs,H-5,H-5'), 11.62 (lH,s,HO-)
MS, m/z 360 (M+,0.5%), 197 (7), 196 (67), 180
(6), 179 (51), 178 (100), 166 (6), 165 (66), 164
(45),163 (39), 151 (7),150 (7), 149 (35), 137 (6),
co-o 136 (29), 135 (26), 123 (5), 121 (16),120 (30), 109
(8), 108 (13), 107 (24), 93 (5),92 (6), 91 (16)
OH StL: Pseudocyphellaria norvegica (Gyelnik)
P.James
TLC: RF A: 0.39, B: 0.54, C: 0.36
Me
7'"
4' -0-Methylnorcryptochlorophaeic acid Physical data unknown

(4'-O-Methylnorcryptochlorophaesaure) StL: Ramalina americana Hale
Lit: c.P. Culberson et al. 1990a
C2sH320S (460.51)
5"
Me 4'-0-Methylnorhomosekikaic acid
(4' -O-Methylnorhomosekikasaure)
CZ3H2S0S (432.45)
OH
CO-O 3"
HO
3
OH MeO ~,,, OH
~CO-O
HO 5 OH MeO
3
Microcrystals (CHC13-CC14), mp 160C
React: NaOCl red
IH-NMR (CDC13-acetone-d6 ): 0.80, 0.88 (2x3H,
2xt,J=6.0, 6.7Hz,Me-5",Me-5 111 ), 1.20-1.40 (8H,
Crystals (CHC13 -CC14), mp 176C
m,4x-CH 2-), 1.56-1.81 (4H,m,-CH 2-4",-CH 2-
React: NaOCl red
4111 ), 3.02, 3.04 (2x2H,2xt,J=7.3Hz,-CH z-1",-
IH-NMR (CDC13 -acetone-d6 ): 0.97 (6H,bt,Me-
CH2-1 111 ), 3.88 (3H,s,MeO-), 6.34,6.36 (2x1H,
3",Me-5 111 ), 1.10-2.00 (8H,m,4X-CH 2-), 2.80-
2xd,J=2.3Hz,H-3,H-5), 6.43 (1H,s,H-5'), 11.20,
3.22 (4H,m,-CH 2-1",-CH 2-1 111 ), 3.91 (3H,s,
12.23 (2x1H,2xs,2x-OH)
MeO-), 6.38 (2H,s,H-3,H-5), 6.53 (lH,s,H-5'),
MS, m/z 252 (0.2%),210 (31), 180 (17), 167 (8),
10.0 (bs,-OH,-COOH)
154 (51), 153 (100), 139 (7), 138 (13), 137 (10),
MS, m/z 254 (10), 237 (11), 236 (67),218 (6),200
125 (8), 124 (84), 123 (24), 122 (6), 110 (7)
(28),196 (29),195 (11), 193 (8), 190 (11),180 (7),
StL: Cladonia merochlorophaea Asah.
179 (46), 178 (100), 167 (15), 163 (12), 162 (11),
TLC: A: 36, B': 48, C: 34
154 (50), 153 (93), 152 (14), 151 (20), 150 (37),
HPLC: RI 34 149 (13),147 (9), 139 (8), 138 (10), 137 (10),136
Lit: Elix and Wardlaw 1986
(13), 135 (10), 134 (32), 133 (5), 124 (19)~ 123
(21), 122 (31), 121 (49), 110 (8), 108 (9), 107 (8)
2-0-Methylnordivaricatic acid StL: Ramalina luciae Molho, Bodo, W.Culb. et
(2-0-Methylnordivaricatsaure) C.Culb.
TLC: A: 39, B': 46, C: 32
C21 H240 7 (388.40)
HPLC: RI 24
Me Lit: Molho et al. 1981; Elix et Wardlaw 1986
~ CO-O'((OH 2-0-Methylnorimbricaric acid
HO~OM. ~ COOH
(2-0-Methylnorimbricarsaure)
C23H2S07 (416.75)
Me
3.16 Depsides 279
MS, m/z 183 (5%), 182 (51), 166 (5),165 (54),164

(100),163 (6),138 (8),137 (5),136 (13), 135 (22),
134 (7), 122 (10), 121 (19), 109 (7), 108 (7), 107
(21), 106 (19)
StL: Pseudocyphellaria norvegica (Gyelnik)
HO
3
, :::0::6:::0"
l/f{~
P.James
TLC: RF A: 0.27, B: 0.48, C: 0.30
MI? 4'-0-Methylnorsekikaic acid

3 111 (4'-0-Methylnorsekikasaure)
Needles (cyclohexane-toluene), mp 124-125C C21 H 2Ps (404.40)

lH-NMR (CDCI 3): 0.89-1.02 (6H,m,Me-5",Me-
3"
3111 ), 1.23-1.33 (8H,m,-CH 2-2"-4", -CH 2 -2 111 ), Me
2.67 (2H,bt,-CH 2-1"), 2.98 (2H,bt,-CH 2-1 111 ) ,
3.87 (3H,s,-OMe), 6.34, 6.35 (2x1H,2xd,J=
2.1Hz,H-3,H-5), 6.66, 6.79 (2x1H,2xd,J=2.4Hz, s~, co_o~QHC~QH
H-3',H-5'), 11.54 (1H,s,-OH)
MS, mlz 238 (17%),221 (72), 196 (29), 182 (50), HO~OH 3
MI?O
5
,1
178 (100), 177 (37), 150 (41), 138 (45), 137 (32), Me
124 (54), 123 (50), 122 (40) 3'"
Crystals (acetone), mp 159-161, 182C (CHCI3 -
CCI4 )
React: NaOCI red
2'-0-Methylnorobtusatic acid IR (KBr): 1140, 1190, 1255, 1505, 1620, 1645,
(2' -0-Methylnorobtusatsaure) 1660, 2870, 2960, 3360cm-1
lH-NMR (80 MHz,CDCI 3): 0.98 (6H,m,Me-3",
ClsH1S07 (346.32)
Me-3 111 ) , 1.67 (4H,m,-CH 2-2",-CH2-2 111 ) , 2.91
*
(4H,t,-CH 2-1",-CH2-1 111 ) , 3.89 (3H,s,-OMe),
MI?
6.31 (2H,s,H-3,H-5), 6.45 (1H,s,H-5'), 10.94"
CO-O 3' OMI?
11.49 (s,2x-OH,-COOH)
"0 . 0" ;yeCOO"

MI? MI?
MS, m/z 404 (M+,O.l %), 386 (0.2), 360 (1), 330
(1),227 (2),226 (18),209 (10),208 (36),207 (2),
197 (3), 196 (31), 183 (6), 182 (49), 181 (3), 180
(7),179 (50), 178 (75), 163 (5), 162 (11),154 (13),
Needles (EtOAc-n-pentane), mp 191-193C 153 (100), 152 (16), 151 (5),150 (13),138 (5), 137
React: N aOCI red (7), 124 (23), 123 (15), 122 (7), 121 (15), 110 (3),
lH-NMR (CDCI3 -acetone-d6 ): 2.11, 2.42, 2.59 44 (30)
(3x3H,3xs,3xMe-), 3.87 (3H,s,MeO-), 6.38 Deriv: Methyl 2'-0-methylsekikate, mp 102C
(1H,s,H-5), 6.68 (2H,s,H-3',H-5'), 11.47 (s,- (acetone), from 4'-0-methylnorsekikaic acid
OH). with CH 2N2 in 12h
StL: Ramalina farinacea (1.) Ach. (from Piji) 71/

TLC: A: 35, B': 29, C: 27 Me
HPLC: R, 20
Lit: Mollio et al. 1979; Elix and Wardlaw 1986
2-0-Methylnorstenosporic acid
3'
(2-0-Methylnorstenosporsaure) 1 CO-O .................... ./
C23H2S07 (416.45) OMe

3
3"
Me
~111 3'
OH
~CO-O Me
HO 5 3 OM. 5' COOH
7'"
Needles (cyclohexane-toluene), mp 85-8rC
IH-NMR (CDC13): 0.90-0.93 (6H,m,Me-7",Me-
7"'), 1.24-1.38 (10H,m,-CH z-2"-6", -CH z-2 111 -
Me 6"'), 2.59, 3.02 (2x2H,2xbt,-CH z-1",-CH z-l"'),
5'" 3.88 (3H,s,-OMe), 6.36, 6.37 (2xlH,2xd,J=
Needles (cyclohexane-toluene), mp 111-113 c 2.1Hz,H-3,H-5), 6.96, 6.82 (2xlH,2xd,J=2.4Hz,
IH-NMR (CDC13): 0.93-1.02 (6H,m,Me-3",Me- H-3',H-5'), 11.49 (1H,s,-OH)
5111), 1.24-1.45 (8H,m,-CH 2-2",-CH2-2 111 -4111 ), MS, m/z 266 (1%), 252 (3), 234 (4), 222 (3),208
2.67 (2H,bt,-CH z-1"), 3.01 (2H,bt,-CH z-1 111 ), (15), 182 (8), 168 (8), 150 (ll), 138 (32), 124
3.88 (3H,s,-OMe), 6.35, 6.36 (2x1H,2xd,J= (100), 107 (5)
2.1Hz,H-3,H-5), 6.68, 6.80 (2XIH,2xd,J=2.4Hz, StL: not yet found in lichens
H-3',H-5'), 11.47 (1H,s,-OH) Lit: Elix et al. 1991c
MS, m/z 224 (12%), 210 (17), 206 (19),193 (73),
180 (12), 178 (17), 177 (47), 168 (15), 150 (50), 2'-0-Methylnorsuperphyllinic acid
138 (25), 124 (100), 122 (27), 121 (78) (2' -O-Methylnorsuperphyllinsaure)
TLC: A: 34, B': 43, C: 29 C33H 44 0 9 (584.68)
HPLC: R, 26
Lit: c.P. Culberson et al1990a; Elix et al. 1991c
2-0-Methylnorsuperlatolic acid
(2-0-Methylnorsuperlatolsaure)
CZ9H4007 (500.51)
3.16 Depsides 281
Me HPLC: Rr 22
Lit: Chester and Elix 1979a
4-0-Methylolivetoric acid
(4-0-Methylolivetorsaure)
CO-O C27H340S (486.54)
OH 7"
Me
CO-O OH
Me
COOH
React: NaOCI red
StL: Stirtonia ramosa Makhija et Patwardhan
TLC: RF A: 0.31, B: 0.27, C: 0.16 Me
HPLC: RF 1.128 (MeOH:HzO:AcOH = 82:18: 5"1
1.6)
Lit: c.P. Culberson et a1. 1990c Needles (toluene-cyc1ohexane), mp 124-125C
React: KOH + NaOCI rose
UV (EtOH): 223 (4.11),269 (4.15), 308nm (3.99)
2-0-Methylobtusatic acid
IR: 1662, 1676, 1679, 3218 cm- 1
(2-0-Methylo btusatsaure)
lH-NMR (100 MHz,CDCI3): 0.7l-1.06 (6H,m,
Cl9Hzo07 (360.35) Me-7",Me-5"'), 1.06-1.88 (12H,m,6x-CH 2-),
2.45 (2H,t,J=8Hz,-CH 2-3"), 2.88-3.13 (2H,m,
Me -CH 2-1"'), 3.85 (3H,s,-OMe), 4.10 (2H,s,-CH 2-
)yCO-O OH
I"), 6.33,6.49, 6.55, 6.88 (4x1H,4xd,J=2Hz"
M'O~OM'
H-3,H-5,H-3',H-5'), 7.42, 9.69 (2H,2xbs,2x-
OH)
YeOOH MS, m/z 280 (4%),263 (13),262 (75),224 (37),
Me Me , 207 (15),206 (100), 191 (7), 180 (10), 178 (30),
177 (30), 168 (35), 165 (14), 164 (98), 163 (22),
Crystals (acetone-toluene), mp 174C 151 (12), 150 (63), 149 (12), 135 (33), 124 (18),
lH-NMR (acetone-d6 ): 2.14, 2.45, 2.68 (3x3H, 123 (11), 122 (22), 121 (18)
3xs,3xMe-), 3.87, 3.93 (2x3H,2xs,2x-OMe), StL: Neofuscelia brattii (Ess1.) Essl.
6.79 (3H,s,H-5,H-3',H-5') TLC: k 44, B: 51, B': 49, C: 48
MS, m/z 360 (M+,<I%), 193 (100), 150 (8) HPLC: Rr 33
StL: Xanthoparmelia tusconensis (Nash) Egan Lit: Culberson and Esslinger 1976; Elix and
TLC: A: 42, B: 56, B': 52, C: 45 Perguson 1978
4'-0-Methyl-2"-oxo-cryptochlorophaeic acid (19),69 (13),65 (14),53 (10), 51 (11),49 (10),43

(4-0-Methyl-2"-oxo-cryptochlorophaesaure) (28),40 (17), 38 (17),29 (17),28 (31),27 (13)
StL: Ramalina asahinae W.Culb. et C.Culb.
C26 H 32 0 9 (488.52)
TLC: A: 35, B: 30, B': 30, C: 22
Me Lit: Chester and Elix 1978
OH 2-0-Methylperlatolic acid
CO-O (2-0-Methylperlatolsaure)
MeO OMe HO
CZ6H3407 (458.53)
5"
Me
Me

StL: Ramalina subfraxinea Nyl. (a race from
CO-O OH
New Caledonia)
Lit: c.P. Culberson et al. 1990b MeO COOH
3
4'-0-Methylpaludosic acid
(4' -O-Methylpaludossaure)
Me
C24H300S (446.48) 5'"
3" Plates (cyclohexane-n-pentane), mp 94-95C
IH-NMR (60MHz,CDCU: 0.84-1.04 (6H,m,Me-
~
Mel" OH 5",Me-5"'), 1.25-1.82 (12H,m,6x-CH 2-), 2.72,
CO--O 3.03 (2x2H,2xbt,-CH 2-1",-CH2-1"'), 3.83, 3.86
(2x3H,2xs,2x-OMe), 6.41 (2H,s,H-3,H-5), 6.70,
HO 5 3 OMe MeO 6.83 (2xlH,2xd,J=2.5Hz,H-3',H-5'), 9.80, 11.30
(2H,2xbs, -0 H,-COO H)
MS, m/z 253 (10%),252 (59), 235 (29), 224 (26),
207 (11), 206 (41), 197 (12), 196 (100), 195 (14),
191 (35), 178 (16), 168 (21), 163 (12), 152 (20),
Crystals (acetone-benzene-cyclohexane), mp 151 (14), 150 (32), 127 (12), 124 (25), 123 (10),
138-139C 122 (11), 121 (10)
IH-NMR (100 MHz, acetone-d6): 0.96 (6H,bt, StL: Pertusaria tuberculifera Nyl.
Me-3",Me-5"'), 1.28-1.90 (8H,m,4x-CH z-), TLC: A: 48, B: 60, B': 60, C: 52
2.78, 3.03 (2x2H,2xbt,-CH z-1",-CH 2-1"'), 3.81, HPLC: Rl42
3.93 (2x3H,2xs,2x-OMe), 6.41 (2H,s,H-3,H-5), Lit: c.P. Culberson and Dibben 1972; Elix 1974
6.64 (1H,s,H-5').
MS, m/z 254 (20%), 237 (13), 236 (74),210 (28),
2'-0-Methylperlatolic acid
194 (14), 193 (100), 179 (25), 177 (39), 166 (17),
(2' -0-Methylperlatolsaure)
154 (13), 153 (22), 151 (25), 138 (42), 137 (22),
134 (28), 123 (11), 121 (12), 91 (11), 79 (11), 77 CZ6H3407 (458.52)
3.16 Depsides 283
5" 177 (50), 164 (16), 149 (14), 138 (49), 137 (16),
Me 123 (11)
Deriv: Methyl 2'-O-methylperlatolate, needles
(MeOH), mp 75-76C, from 2'-O-methyl-per-
latolic acid with CH 2N2
7 StL: Pertusaria globularis (Ach.) Tuck.
1 CO-O OMe TLC: A: 48, B: 50, B': 54, C: 61
HPLC: RI 39
OH eOOH Lit: Elix 1974; Huneck and Schreiber 1975; Endo
3
et al. 1994
2' -O-Methylphenarctin
Me C22 H 22 0 9 (430.40)
5'" Me Me
O::*::-~*::M'
Needles (MeOH-H 20), mp 126-127C
React: FeCl3 (EtOH-H 20) brown
UV (MeOH): 220 (4.59), 270 (4.32), 305nm
(3.90) CHO Me
IR (KBr): 715, 780, 808, 836, 864, 908, 950, 965, Plates (CH 2CI 2-n-pentane), mp 166C
1048, 1090, 1120, 1160, 1208, 1250, 1300, 1378, React: PD yellow, NaOCI red
1430, 1470, 1595, 1618, 1654, 1700, 2700, 2980, IH-NMR (200MHz,CDC1 3): 2.18, 2.21, 2.21, 2.75
3500cm-1 (4x3H,4xs,4xMe-), 3.78 (3H,s,-OMe), 3.94 (3H,
IH-NMR (400MHz,CDCI 3): 0.87 (3H,t,J=7.3Hz, s,-COOMe), 10.23, 10.37 (2x1H,2xs, 2x-CHO),
Me-5//), 0.89 (3H,t,J=7.3Hz,Me-5/1f), 1.35 (8H, 13.52, 13.87 (2x1H,2xs,2x-OH)
m,-CH 2- 3//,-CH 2-4//,-CH2-3"',-CH 2-4"'), 1.65 MS, m/z 430 (M+,0.2%), 225 (8), 224 (58), 207
(2H,dddd,J=7.8Hz,-CH 2-2"'), 1.67 (2H,dddd, (14), 194 (12), 193 (100), 192 (23), 178 (17), 177
J=7.8Hz,-CH 2-2//), 2.77 (2H,dd,J=7.8Hz,-CH 2- (12), 163 (8), 151 (5), 150 (11), 149 (7), 135 (6),
1"'), 2.98 (2H,dd,J=7.8Hz,-CH 2-1//), 3.84 (3H, 134 (9), 121 (5), 105 (5)
s,MeO-4) 3.90 (3H,s,MeO-2'), 6.39 (2H,d,J= StL: Pseudocyphellaria pickeringii (Tuck.)
3.2Hz,H-3,H-5), 6.66, 6.71 (2x1H,2xd,J=2.0Hz, D.Gall.
H-3',H-5'), 11.37 (1H,bs,HO-2) TLC: A: 63, B': 32, E: 10
13C-NMR (100MHz,CDCIJ: C-1: 103.73, C-2: Lit: Elix et al. 1987h
166.54, C-3: 99.03, C-4: 164.88, C-4-0Me:
55.43, C-5: 111.40, C-6: 148.44, C-7: 169.86a , C-
1': 119.68, C-2': 157.95, C-2' -OMe: 56.39, C-3': 2'-O-Methylpseudocyphellarin A
103.13, C-4': 151.92, C-5': 115.23, C-6': 144.77, C22 H 2P8 (416.41)
C-7: 170.15", C-l//: 37.32, C-2//: 32.10b, C-3//:
32.11 b , C-4//: 22.66 c, C-5': 14.05, C-l"': 33.88, C-
2"': 30.71, C-3"': 31.67, C-4"': 22.40 c, C-5"': 13.95. Me*Me c o _ o * M eOMe
Values marked with a,b and c may be exchanged
MS, m/z 239 (11%),238 (73),221 (25),220 (15), HO OH Me COOMe
195 (10), 183 (11), 182 (100), 181 (21), 178 (24), CHO Me
Plates (CH 2Clz-n-pentane), mp 190C 2-0-Methylsekikaic acid

React: PD yellow, NaOCI red (2-0-Methylsekikasaure)
IH-NMR (200MHz,CDCI3): 2.07, 2.11 2.19,2.22
CZ3H2S0S (432.45)
2.70 (5x3H,5xs,5xMe-), 3.78 (3H,s,-OMe), 3.94
(3H,s,-COOMe), 10.39 (1H,s,-CHO), 12.40, 3"
13.07 (2x1H,2xs,2x-OH) Me
MS, m/z 416 (M+,0.2%), 225 (6), 224 (48), 194 ~lU OH
(12), 193 (100), 192 (31), 191 (5), 178 (6), 177
. : ( ( C O - - OyYCOOH
(10),166 (8),165 (13), 164 (46),163 (9), 150 (10),
149 (7), 136 (12), 135 (10), 134 (9), 121 (6), 108 MeO 3 OMe Meo~
(5), 107 (8)
Me
StL: Pseudocyphellaria pickeringii (Tuck.) 3'"
D.Gall.
TLC: A: 71, B': 59, E: 52 Crystals (benzene-cyclohexane), mp 156-157C
Lit: Elix et al. 1987h IH-NMR (100MHz,acetone-d6 ): 0.88-1.08
(2x3H,m,Me-3",Me-3"'), 1.48-1.86 (4H,m,2x-
CH z-), 2.70-3.14 (4H,m,-CH z-l",-CH z-1"'),
Methyl sekikate (Sekikasauremethylester) 3.85 3.87 3.96 (3x3H,3xs,3x-OMe), 6.53 (2H,s,
Cz3H28 0 S (432.45) H-3,H-5), 6.66 (1H,s,H-5')
MS, m/z 224 (5%), 208 (17),207 (100), 181 (8),
*:
3" 135 (5),44 (9), 28 (23)
StL: Ramalina asahinae W. Culb. et C. Culb.
~'"
TLC: A: 41, B: 31, B': 40, C: 43
HPLC: RI 25
~CO-O ~~OMe Lit: Chester and Elix 1978
MeO 3 OH MeO 5' 1
Me 2-0-Methylsquamatic acid
3'" (2-0-Methylsquamatsaure)
Crystals (MeOH-HzO), mp 124C CZOHZ009 (404.36)
React: FeCl3 (EtOH) red
UV (MeOH): 219,260, 299nm
MeO*::O*::OH
IR (KBr): 1656, 1740, 2908-2950 cm- 1
IH-NMR (100MHz,CDCU: 0.85 (6H,m,2xMe-),
1.6 (4H,m,2x-CH 2-), 2.8 (4H,m,-CH 2-1",-CHz-
1"'),3.68,3.73 (2x3H,2xs,2x-OMe), 3.85 (3H,s,- eOOH Me
COOMe), 6.14, 6.24 (3H,3xarom.-H)
Microcrystals (acetone-EtOAc), mp 216-220 c
MS, m/z 432 (M+), 208, 193, 182, 179, 166, 153,
IH-NMR (60MHz,acetone-d6 ): 2.17, 2.40, 2.53
151
(3x3H,3xs,3xMe-), 3.83, 3.90 (2x3H,2xs,2x-
StL: Protousnea dusenii (Du Rietz) Krog
OMe), 6.60-6.80 (2H,m,H-5,H-5')
TLC: A: 72, B': 62, C: 77, E: 53
MS,m/z 365 (1 %),343 (0.1),237 (0.8),223 (100),
Lit: Titze 1987
209 (10), 193 (10), 179 (24)
Deriv: Methyl 2,2' -di-O-methylsquamatate,
amorphous powder (EtOAc-n,-hexane), from 2-
3.16 Depsides 285
O-methylsquamatic acid with CH2N2, IR: 840, 3"
~
1100, 1260, 1600, 1650, 1730cm-1 Me,,,
StL: Protousnea magellanica (Mont.) Krog
3'
TLC: A: 15, B': 25, C: 23, G: 37 eo-o OMe
HPLC: Rj 13
Lit: Garbarino et al. 1987 MeO 5 OH 5' eOOH
3
2-0-Methylstenosporic acid
(2-0-Methylstenosporsaure)
Me
C24 H 30 0 7 (430.48) 5 lll
1
Me Microcrystals (CH 2CI2-n-pentane), mp 12rC
(softens at 109C)
IH-NMR (CDCI 3 ): 0.97 (6H,bt,Me-3",Me-5"'),
eo- 0 OH 1.14-2.41 (8H,m,4x-CH 2-), 2.72-3.09 (4H,m,-
CH 2-1",-CH 2-1"'), 3.84 3.90 (2x3H,2xs,2x-
MeO OMe eOOH OMe), 6.38 (2H,s,H-3',H-5'), 6.67, 6.71 (2x1H,
2xd,J=2Hz,H-3,H-5), 11.35 (s,-OH)
MS, m/z 430 (M+,0.2%), 239 (8), 238 (51), 221
(13),210 (9), 195 (10), 194 (8), 193 (37), 192 (36),
Me 191 (6),183 (10), 182 (100), 181 (27), 180 (5), 178
(12),177 (61),167 (6),165 (8), 164 (20),163 (5),
Rod-shaped crystals (cyclohexane), mp 112C
151 (9), 149 (6), 139 (5), 138 (38), 137 (20), 136
IH-NMR (CDCI3): 0.75-1.13 (6H,m,2x-Me),
(5), 135 (21), 123 (11)
1.13-1.96 (8H,m,4x-CH 2-), 2.70 (2H,bt,J=7.5Hz,
StL: Physcidia cylindrophora (Tayl.) Hue
benzyl.-CH2-), 2.85-3.22 (2H,m,benzyl.-CH2-),
TLC:A:4~B~49,C:59
3.87, 3.90 (2x3H,2xs,2xMeO-) 6.42 (2H,s,H-3,
HPLC: RI 36
H-5), 6.76, 6.82 (2H,d,J=2.5Hz,H-3',H-5'),
10.65 (2H,bs,-COOH,HO-)
MS, m/z 386 (0.1 %),224 (1), 208 (13),207 (100),
191 (2), 177 (2) 2-0-Methylsulphurellin
StL: Ramalina sayreana W. Culb. et C. Culb.
TLC: A: 49, B: 56, B': 56, C: 48 CZ6H3zClz07 (527.43)
HPLC: RI 35
Lit: W.L. Culberson and C.P. Culberson 1981;
Elix et al. 1985c
el eo-o OM~
2' -O-Methylstenosporic acid HO OM~ eOOH

(2'-0-Methylstenosporsaure)
el
C24H3007 (430.48)
M~

MS, mlz 291, 289, 239 2'-O-Methylsuperlatolic acid

StL: Lecanora jamesii Laundon (2'-0-Methylsuperlatolsaure)
TLC: A: 44, B': 49, C: 46
C30H4Z07 (514.64)
Lit: Elix and Ernst-Russell 1993
Me 7"
2-O-Methylsuperlatolic acid
(2-0-Methylsuperlatolsaure)
C30H4207 (514.64)
7"
Me
3
OH
OH
Me
eOOH 7m
Crystals (EtOAc-n-hexane), mp 114-ll5C

IH-NMR (CDCI3 ): 0.84, 0.88 (2x3H,2xbt,J=7Hz,
Me-7",Me-7"'), 1.20-1.74 (20H,m,10x-CH 2-),
2.78 (2H,t,J=7.9Hz,-CH z-1"), 2.97 (2H,t,J=
Me 7.8Hz,-CH z-1"'), 3.85, 3.91 (2x3H,2xs,2x-OMe),
7 Iff 6.39 (2H,s,H-3',H-5'), 6.67, 6.72 (2x1H,2xd,
J=2.1Hz,H-3,H-5), 11.41 (s,-OH)
Crystals (cyclohexane), mp 71-72C MS, m/z 266 (10%), 222 (10), 182 (42), 181 (8),
IH-NMR (CDCU: 0.87, 0.89 (2x3H,2xt,J=6.6, 177 (18), 151 (14), 139 (9), 138 (100), 137 (24),
6.7Hz, Me-7",Me-7111 ), 1.30, 1.40, 1.65 (20H, 123 (10)
3xm,-CH2-2" -6",-CH z-2'" -6 111 ), 2.69, 3.00 (2x StL: Biatora sorediosa Rambold
2H,2xm,-CH 2-1",-CH z-1"'), 3.84, 3.87 (2x3H, TLC: A: 54, B': 61, C: 66
2xs,2x-OMe), 6.38 (2H,d,J=2.3Hz,H-3',H-5'), HPLC: Rr 48
6.73 (2H,d,J=2.3Hz,H-3,H-5), 11.30 (lH,s,HO-) Lit: Elix and David 1991
MS, mlz 264 (17%),263 (100), 196 (15)
StL: Pertusaria follmanniana Archer et Elix,
Pertusaria modesta Miill.-Arg. 4-0-Methylsuperolivetoric acid
TLC: A: 46, B: 66, C:64 (4-0-Methylsuperolivetorsaure)
HPLC: Rr 50 C31H420S (542.65)
3.16 Depsides 287
Physical data unknown, only microchemically

identified
StL: Porpidia glaucophaea (Koerb.) Hertel
et Knoph, Pseudobaeomyces pachycarpa
(Miill.Arg.) Sato
TLC: A: 43, B': 32, C: 44
Lit: c.P. Culberson et al. 1987
OH Microphyllinic acid (Microphyllinsaure)

C29H3609 (528.58)
Ml>
Ml>
Physical data unknown, only micro chemically
identified
StL: Pseudobaeomyces pachycarpa (Miill.Arg.) CO-O
Sato
TLC: B: 61, C: 63 OH
HPLC: R[ 42
Lit: c.P. Culberson et al. 1987; Elix and Ernst-
Russell 1993
2'-O-Methylsuperphyllinic acid
(2'-O-Methylsuperphyllinsaure) Needles (benzene-n-hexane), mp 116C
C33H4609 (586.70) React: PeCl3 violet
Deriv: Methyl microphyllate, needles (EtOH),
Me
mp 118C, from microphyllinic acid with CH2N2
in Et 20 at OC in 30s
MS, m/z 280, 262, 244
StL: Cetrelia japonica (Zahlbr.) W.Culb. et
C.Culb.
TLC: A: 41, B: 39, C: 41
HPLC: R[ 30
MC: Pig. 30D
OH Lit: c.P. Culberson 1969
Me
Miriquidic acid (Miriquidisaure) Nephroarctin

C2sH300S (458.49) C2oH2007 (372.36)
10 8'
Me Me
3'
OH~*lo-o*'
9'
. OMe
l'
OH HO OH Me
COOH CHO Me
OH 8 10'
3
Prisms (acetone), mp 192-193,200-201 c

React: KOH yellow, PD yellow, NaOCI red
Me UV (EtOH): 238 (3.81), 281 (4.09), 315 (4.00),
5'"
379 nm (3.54).
Needles (benzene), mp 140-141 c IR (KBr): 1630, 1740cm-1
React: FeCl3 (EtOH) violet IH-NMR (400MHz,DMSO-d6 ): 2.05 (3H,s,Me-
UV (MeOH): 219 (4.55), 269 (4.31), 308nm 8'), 2.08 (3H,s,Me-IO'), 2.28 (3H,s,Me-9'), 2.71
(4.12) (3H,s,Me-l0), 3.78 (3H,s,MeO-2'), 6.79 (1H,s,
IR (KBr): 740, 810, 850, 865, 968, 1024, 1050, H-l'), 10.20 (1H,s,CHO-8), 10.24 (1H,s,CHO-
1090, 1120, 1148, 1162, 1210, 1250, 1330, 1380, 9)
1418, 1445, 1465, 1580, 1608, 1640, 1690, 2950, MS, m/z 372 (M+,6%), 207 (30), 166 (100), 151
3100,3450 cm- 1 (20)
MS, m/z 252 (19%),234 (15), 224 (12), 208 (25), StL: Nephroma arcticum (1.) Torss.
206 (19), 195 (12), 190 (12), 178 (29), 151 (IOO), TLC: A: 70, B: 53, B': 52, C: 63, E: 21
137 (23), 124 (37), 77 (9),69 (11),44 (65) HPLC: R] 34
Deriv: Methyl miriquidate, needles (MeOH), MC: Fig. 31B
from miriquidic acid with CH2N2 in Et20 at OC Lit: Nuno et al. 1969; Bruun 1971a; Hamilton
in 30s and Sargent 1976
IH-NMR (90MHz,CDCI3 ): 0.90-1.20 (6H,m,Me-
5",Me-5/f1), 1.20-1.80 (6H,m,3x-CH 2-), 2.37
Nordivaricatic acid (Nordivaricatsaure)
(2H,q,-CH 2-4"), 2.91 (2H,t,-CH 2-1/f1), 3.26 (2H,
t,-CH 2-1"), 3.82 (2H,s,-OMe), 3.97 (3H,s,- C2oH2207 (374.38)
COOMe), 6.38 (2H,s,H-3',H-5'), 6.57, 6.70 (2x
1H,2xd,J=2.45Hz,H-3,H-,-5), 11.98, 12.10 (2xlH, 3"
2xs,2x-OH) Me
StL: Lecidea Zeucophaea (Flk.) Nyl. 1"
TLC: A: 42, B: 48, B': 46, C: 44 5 CO-O 3' OH
HPLC: Rr 30
MC: Fig. 31A
Lit: Huneck et al. 1971; Elix and Jayanthi 1986
Me
3'"
3.16 Depsides 289
N"eedles (CHCl3-CCl4-n-hexane), mp 126-128 c 5"

React: NaOCl red, FeCl3 (EtOH) violet Me
IH-NMR (100MHz,CDCl3 ): 0.82-1.14 (6H,m, 4"
Me-3",Me-3"'), 1.48-1.90 (4H,m,-CH z-2",
-CHz-2"'), 2.82-3.22 (4H,m,-CH z-l",-CHz-l"'),
6.40 (2H,s,H-3',H-5'), 6.68, 6.80 (2xlH,2xd,
J=3Hz,H-3,H-5), 9.20, 11.50 (2xlH,2xbs,2x- HO
OH)
MS, m/z 374 (M+,0.6%), 197 (5), 196 (37), 179
(21), 178 (100), 163 (8), 152 (15), 150 (32), 137
(9), 124 (5), 123 (17), 122 (24), 121 (46),94 (7),91 Me
(8),79 (6),77 (10) 5 111
StL: Heterodea beaugleholei R. Filson, Neo-
fuscelia verrucella (Ess1.) Ess1. Prisms (acetone-cydohexane), mp 137C
TLC: A: 33, B: 55, B': 52, C: 29 React: NaOCl red
HPLC: RJ 22 IH-NMR (acetone-d6): 0.96 (6H,t,J=7Hz,Me-
Lit: C.F. Culberson et a1. 1997a; lix and Tearne 5",Me-5"'), 1.26-1.68 (6H,m,-CH z-2'" -4"'), 2.38
1977 (2H,q,J=7Hz,-CH z-4"), 2.66-3.24 (6H,m,-CH z-
1",-CHz-2",-CH z-1"'), 6.16, 6.24, 6.52, 6.60
(4H,4xd,J=2.5Hz,H-3,H-5,H-3',H-5'), 8.76 (1H,
Nor-iso-obtusatic acid (Nor-iso-obtusatsaure) bs,-COOH)
C17H1607 (332.30) MS, m/z 221 (5%),220 (21),207 (7), 192 (2), 180
(12), 164 (50), 163 (74), 137 (100)
StL: Lecidea leucophaea (Flk.) Ny1.
~CO-O~OH TLC: A: 31, B': 38, C: 23
HPLC: RJ 21
HO~OH ~COOH Lit: lix and Jayanthi 1986
Me
Physical data unknown Norobtusatic acid (Norobtusatsaure)

React: NaOCl red C17H1607 (332.30)
Me
Lit: C.F. Culberson et a1. 1990a
NCO-OyyOH
Normiriquidic acid (Normiriquidisaure) HO~OH leooH
C24 HzsOs (444.46) Me Me

identified
React: NaOCl red
MS, mlz 332 (M+), 182, 168, 165
StL: Hypothrachyna chicitae (Hale) Hale
Lit: C.F. Culberson and Hale 1973b; Elix and
Ernst-Russell 1993
Obtusatic acid (Obtusatsaure) Olivetoric acid (Olivetorsaure)

ClsHlS07 (346.32) CZ6H3Z0S (472.52)
*
9 7"
Me Me
CO-O 3' OH
Mea 5 OH ~COOH
Me Me ,
8 8' CO-o 3
OH
Needles (acetone), mp 208-209 DC (dec.) OH COOH

React: NaOCllight yellow, PeC13 purple 3
UV (MeOH): 214 (4.57), 274 (4.27), 303nm
(3.98)
IR (KBr): 690, 730, 790, 830, 845, 890, 1000, 1030, Me
1060, 1l05, ll55, 1208, 1265, 1300, 1350, 1410, 5 III
1464, 1510, 1570, 1610, 1650,3100, 3500 cm-l
IH-NMR (60MHz,DMSO-d6-acetone-d 6): 2.01, Needles (benzene), mp 151 DC
2.55 (9H,2xs,Me-8,Me-9,Me-8'), 3.88 (3H,s,- React: NaOCl red, PeC13 purple
OMe), 6.54 (1H,s,H-5), 6.68, 6.74 (2xlH,2xd, UV (MeOH): 270 (4.16), 305nm (4.ll)
J=2.5Hz,H-3',H-5') IR (KBr): 710, 760, 800, 830, 850, 862, 894, 1020,
MS, m/z 346 (M+,3%), 196 (25), 180 (13), 179 1030, 1060, ll40, ll65, 1200, 1250, 1300, 1410,
(100),178 (39), 177 (7),168 (8), 152 (5),151 (15), 1450, 1500, 1620, 1650, 1690, 2900, 2950, 3150,
150 (67), 149 (ll), 148 (8), 135 (8), 123 (6), 122 3400 cm-l
(20), 121 (7), 107 (12),94 (7), 91 (12), 79 (12), 78 IH-NMR (200MHz,CDC13): 0.75-1.0 (6H,m,Me-
(6),77 (14), 69 (7),67 (7),66 (8),65 (10), 55 (5), 7",Me-5"') , 1.00-1.75 (12H,m,6x-CH z-), 2043
53 (9), 51 (7), 44 (8), 43 (l0) (2H,t,-CH z-3"), 2.98 (2H,t,-CH 2-1"'), 4.07 (2H,
Deriv: Methyl obtusate, needles (MeOH), mp s,-CH z-l"), 6.26, 6.66 (2XIH,2xd,J=2.5Hz,
175 DC, from obtusatic acid with CHzN z in EtzO 2xarom.-H), 6.53, 6.66 (2xlH,2xd,J=2.5Hz,
at ODC in 1 min 2xarom.-H)
13C-NMR (25.05MHz, CDC13): C-l: 104.7, C-2: MS, mlz 248 (25%),224 (20), 206 (35),192 (15),
162.8, C-3: ll1.4, C-4: 162.3, C-5: 106.5, C-6: 168 (25), 150 (100), MS, m/z 472 (M-, 10%),471
140.5, C-7: 169.8, C-8: 7.7, C-9: 23.9", C-4- (30),247 (100), 223 (100),206 (l00), 167 (100),
OMe: 55.5, C-l': 1l0A, C-2': 164.3, C-3': 108.7, 150 (l00)
C-4': 154.2, C-5': ll6.5, C-6': 143.3, C-7': 171.5, Deriv: Methyl olivetorate, needles (MeOH), mp
C-8': 24.7', 7' -COOMe: 52.0; values marked 134 DC, from oliveto ric acid with CHzN z in EtzO
with a may be exchanged at ODC in 30s
StL: Ramalina obtusata (Am.) Bitt. StL: Cetrelia oliveto rum (Nyl.) W.Culb. et
TLC: A: 40, B: 64, B': 61, C: 47 C.Culb., Pseudevernia furfuracea (1.) Zopf
HPLC: RJ 32 TLC: A: 29, B: 37, B': 39, C: 25
MC: Pig. 31C,D; 32A HPLC: RJ 27
Lit: c.P. Culberson 1969; Elix and Norfolk MC: Pig. 32B,C
1975b; Sundholm and Huneck 1981 Lit: c.P. Culberson 1969; Elix and Perguson 1978
3.16 Depsides 291
Oxostenosporie acid (Oxostenosporsaure) Needles (benzene), mp 158.5-159.5, 170-171C

(cyclohexane-benzene-EtOAc)
CZ3Hz60S (430.44)
React: NaOCl red, KOH slowly turning wine red
1
3" UV (EtOH): 216.5, 253, 290nm
IR (Nujol): 1225, 1585, 1625, 1645, 1720, 1735,
Me
3470cm-1
," 3'
CO-O OH IH-NMR (60MHz,CDCl3-acetone-d6): 0.96 (6H,
bt,Me-3",Me-5"'), 1.23-1.90 (8H,m,4x-CHz-),
MeO 5 OH 5' 2.72, 2.96 (2x2H,2xbt,-CH 2-l'-',-CHz-1"') 3.91
3
(3H,s,-OMe), 6.44 (3H,bs,H-3,H-5,H-5'), 7.42
(3H,bs,3x-OH,-COOH)
MS, m/z 241 (5%),240 (25),223 (16),222 (100),
Me 210 (5), 196 (21), 193 (5), 179 (11), 177 (7), 167
S"' (6),166 (24), 165 (25), 153 (6), 151 (7), 140 (32),
Prisms (MeOH), mp 119-120C 139 (42),138 (34), 137 (25), 91 (8),81 (6),79 (7),
IH-NMR (CDCl3): 0.95 (3H,t,J=6.7Hz,Me-3"), 77 (11), 69 (11),67 (9), 65 (8),55 (6),53 (9),51
1.01 (3H,t,J=6.5Hz, Me-5"'), 1.44-1.81 (4H,m, (7),44 (44)
2x-CH z-), 1.90 (2H,t,J=7.3Hz,-CH z-3 111 ), 2.94 StL: Ramalina paludosa B. Moore
(2H,t,J=8Hz,-CH z-1"), 3.22 (2H,s,-CH z-1"'), TLC: A: 39, B: 35, B': 42, C: 33
3.83 (3H,s,-OMe), 6.38 (2H,s,H-3,H-5), 6.63 HPLC: R] 17
(1H,d,J=0.7Hz,H-3'), 6.75 (1H,d,J=0.7Hz,H-5'), Lit: C.F. Culberson 1969; Elix and Norfolk 1975a
11.2 (3H,bs,3x-OH)
MS, m/z358 (1 %),262 (1),238 (1),221 (15),220 Patagonie acid (Patagonsaure)
(100),210 (21), 193 (42), 192 (66), 177 (32), 164
(16), 163 (22), 150 (54), 138 (12), 135 (23), 121 CZSH300S (458.49)
it
(26)
Me
StL: Neofuscelia pulla (Ach.) Essl. 3'
TLC: A: 41, B: 43, B': 46, C: 41 5 1 CO-O ,
HPLC: R] 28
Ml:'O OH 5
Lit: C.F. Culberson et al. 1977a; Elix and Whitton 3
1989
Paludosie acid (Paludossaure)

CZ3HzsOs (432.45)
1
3" Me
9"
Me1 OH
" Cream crystals (EtOAc), mp 104-105C
CO-O
IH-NMR (CDCl 3): 0.90 (3H,m,Me-9"), 1.27-1.54
HO 5 3 OMe HO
(1 OH,ni,-CH 2-4" -8"), 1.98 (2H,bt,-CH z-3"),
2.64 (3H,s,-Me), 3.13, 3.36 (2x1H,2xd,J=16.5Hz,
-CH z-1"), 3.86 (3H,s,-OMe), 6.37, 6.48 (2x1H,
Me 2xd,J=2.2Hz,H-3',H-5'), 6.66, 6,78 (2x1H,2xd,
5'"
J=2Hz,H-3,H-5), 11.19, 11.29 (2xIH,2xs,2x- I': 110.9, C-2': 165.1, C-3': 109.2, C-4': 154.9, C-
OH) 5': 116.5, C-6': 149.3, C-7': 173.2, C-1111: 36.8, C-
MS, m/z 277 (7%), 276 (37), 193 (5), 192 (43),165 2111: 32.6, C-3 111 : 32.3, C-4111: 23.0, C-5"': 14.3
(9), 164 (24), 163 (23), 151 (11), 150 (100) MS, m/z 238 (39%),224 (21), 221 (11),220 (50),
StL: Bunodophoron patagonicum (Dodge) 206 (31), 194 (19) 192 (31), 191 (15), 182 (46),
Wedin 180 (17), 178 (21), 177 (21), 168 (20), 165 (13),
TLC: RF A: 0.38, B: 0.47, C: 0.42 164 (100), 163 (15), 152 (10), 151 (14), 150 (38),
HPLC: RI 0.42 149 (12), 138 (82), 137 (25), 135 (24), 124 (61),
Lit: Elix et aL 1994f 123 (23), 122 (15), 121 (13),77 (15), 69 (14), 65
(11),55 (11),53 (10),51 (13),43 (34)
Deriv: Methyl di-O-methylperlatolate, needles
Perlatolic acid (Perlatolsaure)
(MeOH), mp 5rC, from perlatolic acid with
CZSH3Z07 (444.51) MeJ-KzC0 3
StL: Cetrelia cetrarioides (Del. ex Duby) W.Culb.
5/1
Me et C.Culb.
TLC: A: 44, B: 77, B': 75, C: 54
HPLC: RI47
7
MC: Fig. 32D, 33A
CO-O OH Lit: C.F. Culberson 1969; Elix 1974; Sundholm
and Huneck 1981
OH
Phenarctin
Me
5'"
10 8'
Needles (MeOH-HzO), mp 107-108C 9 Me 7 Me
React: FeCl3 (EtOH) violet
UV (MeOH): 213 (4.45), 269 (4.04), 306nm OHC*~
1 CO-O*OH
9 I ,
(3.83) HO OH Me 5' 1 ~OOMe

IR (KBr): 720, 750, 775, 810, 850, 865, 880, 970,
CHO Me
1030, 1050, 1082, 1150, 1165, 1210, 1250, 1290, e 10'
1305, 1320, 1360, 1470, 1610, 1635, 1655, 3000,
3100,3500 cm- I Crystals, mp 167-168C
IH-NMR (270MHz, DMSO-d6 ): 0.83 (3H,t,Me- React: KOH yellow, PD yellow, NaOCI red
5111), 0.84 (3H,t,Me-5")' 1.27 (8H,m,4x-CH z-), UV (EtOH): 254 (4.49), 283 (4.46),313.5 (4.47),
1.53 (4H,m,-CH z-2",-CH z-2 111 ), 2.58 (2H,m,- 376.5nm (4.02)
CH z-1"'), 2.62 (2H,m,-CH z-1"), 3.73 (3H,s, IR (KBr): 1630, 1655, 1750cm-1
MeO-4), 6.35 (2H,d,J=2.5Hz,H-3,H-5), 6.48 IH-NMR (60MHz,CDCI3 ): 2.15 (6H,s,2xMe-),
(lH,d,J=2.5Hz,H-5'), 6.57 (lH,d,J=2.5Hz,H-3') 2.43, 2.70 (6H,2xs,2x-Me), 3.95 (3H,s,-
!3C-NMR (25.05MHz,acetone-d6 ): C-1: 105.0, COOMe), 10.13, 10.28 (2x1H,2xs,2x-CHO),
C-2: 166.4, C-3: 99.7, C-4: 165.5, C-5: 111.5, C- 10.93, 13.42, 13.77 (3x1H,3xs,3x-OH)
6: 148.8, C-7: 169.8, C-1": 37.5, C-2": 32.8, C-3": MS, m/z 416 (M+,12%), 210 (60), 207 (75), 178
32.6, C-4": 23.2, C-5": 14.3, C-4-0Me: 55.8, C- (100), 166 (15), 150 (70)
3.16 Depsides 293
StL: Nephroma arcticum (1.) Torss. StL: Lecidea plana (Lahm ex Korb.) Nyl.
TLC: A: 66, B': 42, C: 61, E: 21 TLC: A: 49, B: 38, C: 50
Lit: Bruun 1971a; Hamilton and Sargent 1976 HPLC: Rr 34
MC: Fig. 33B
Lit: Huneck 1965; Elix 1974; Sundholm and
Planaic acid (Planasaure)
Huneck 1981
C27H3607 (472.56)
5" Prasinic acid, Superlatolic acid
Me (Prasinsaure, Superlatolsaure)
C29H4007 (500.61)
7
cO-O
7"
Me
MeO OMe
Me CO-O
5'"
Needles (MeOH), mp 110-111 c MeO OH

3
UV (MeOH): 208 (4.56), 254 (3.70), 282nm
(3.67)
IR (KBr): 730, 790, 810, 830, 890, 930, 945, 980,
1035, 1060, 1080, 1110, 1140, 1150, 1180, 1200,
1220, 1240, 1270, 1290, 1315, 1380, 1420, 1460, Me
1590, 1695, 1735, 2700, 2900, 2950, 3500 cm- 1 7 tiJ
IH-NMR (60MHz,CDC13): 0.85-1.04 (6H,m,Me-
5",Me-5"'), 128-1.84 (12H,m,6x-CH z-), 2.66- Needles (acetone-n-hexane), mp 93-94C
2.90 (4H,m,-CH 2-1",-CH2-1"'), 3.83, 3.87, 3.89 IH-NMR (CDCI3): 0.84, 0.88 (2x3H,2xt,Me-
(3x3H,3xs,3x-OMe), 6.41 (2H,s,H-3,H-5), 6.76 7",Me-7'''), 1.28 (20H,m,lOx-CH 2- ) , 2.93, 2.99
(2H,m,H-3',H-5'), 10.20 (IH,bs,-COOH) (2X2H,2xbt,-CH 2-1",-CH z-l"'-), 3.84 (3H,s,~
13C-NMR (25.05MHz,CDC13): C-l: 115.0, C-2: OMe), 6.38 (2H,s,H-3,H-5), 6.63, 6.75 (2H,
161.8, C-3: 96.1, C-4: 158.4, C-5: 106.0, C-6: 2xd,J=2.5Hz,H-3',H-5'), 11.28 (2H,bs,-OH,-
143.5, C-7: 166.2, C-l": 34.0, C-2": 31.7, C-3": COOH), 11.34 (IH,s,-OH)
31.1, C-4": 22.5, C-5": 13.9; C-2-0Me: 55.9, C- MS, m/z 267 (8%), 266 (50),252 (12), 249 (13),
1': 120.9, C-2': 157.2, C-3': 102.6, C-4': 152.4, C- 248 (62), 234 (16) 222 (15), 208 (13), 206 (IS),
5': 114.2, C-6': 142.5, C-7': 168.2, C-l"': 33.4, 205 (10), 193 (9), 192 (42),191 (21),192 (95), 179
C-2"': 31.5, C-3"': 30.4, C-4"': 22.3, C-5"': 13.9, (12), 178 (26), 177 (39), 168 (19), 165 (16), 164
C-7-COOMe: 52.1, C-2'-OMe: 55.3 (100), 151 (21), 150 (25), 149 (13), 138 (82), 137
MS, m/z 472 (M-,5%), 471 (8), 237 (100), 235 (32), 135 (22), 124 (60)
(25),219 (10) 193 (25) Deriv: Methyl prasinate, needles (n-hexane), mp
Deriv: Methyl plan ate, needles (MeOH-HzO), 37-39C, from prasinic acid with CH 2N 2 in Et2 0
mp 58-60C from planaic acid with CH 2N 2 at 0 c in 1 min
StL: Micarea prasina Pr., Pseudobaeomyces Pseudocyphellarin A

pachycarpa (Mull.Arg.) Sato.
C21 H 22 0 B (402.39)
TLC: RF A: 0.54, B: 0.82, C: 0.64
Lit: c.P. Culberson et al. 1984, 1987; Elix et al. 10 e'
1984b
~e*Mel to-o 3~e2' OH
Prunastric acid (Prunastrisaure) 5 2 9' 4' l' 7'

HO 4 3 OH Me 5' 6' eOOMe
Cl9HISOIO (406.33) CHO Me
8 10'
iJ:
B 8'
Me eOOH Prisms (acetone), mp 173-175C
7 7'
5
eo-o 2' l'
,
Me React: KOH yellow, PD yellow, PeCl3 (EtOH)
3' 6, red-brown, NaOCI red
MeO 3 OH MeO 4' 5' EOOH UV (MeOH): 218 (4.15),250 (4.36), S 270 (4.21),
OH
S 290 (3.96), 342nm (3.30); MeOH + NaOH: 221
(4.29),286 (4.19), S 302 (4.13)
Crystals, mp 170C (dec.) IR (KBr): 740, 782, 810, 852, 890, 926, 942, 1010,
UV (MeOH): 228, 264, 298 nm 1030, 1070, 1092, 1116, 1190, 1290, 1312, 1428,
IR (KBr): 610, 660, 700, 840, 940, 1020, 1050, 1640,2980,3400cm-1
1160, 1270, 1300, 1350, 1380, l420, 1450, 1480, IH-NMR (270MHz,DMSO-d6 ): 2.05 (6H,s,Me-
1540, 1580, 1630, 2800, 3300, 3500 cm- l 8',Me-10'), 2.08 (3H,s,Me-10), 2.13 (3H,s,Me-
IH-NMR (90MHz,DMSO-d6 ): 1.75, 2.50 (2x3H, 9'), 2.38 (3H,s, Me-9), 3.82 (3H,s,7'-COOMe),
2xs,2xMe-), 3.20 (3H,s,MeO-), 3.30 (1H,s,- 10.25 (lH,s,CHO-8)
OH), 3.75 (3H,s,-OMe), 4.10 (lH,s,-OH), 6.05 J3C-NMR (50.32MHz,CDCI3 ): C-1: 102.9, C-2:
(2H,d,H-3,H-5), 16.3 (2H,s,2x-COOH) 167.0, C-3: 108.0, C-4: 166.1, C-5: 118.2, C-6:
J3C-NMR (22.11MHz,DMSO-d 6): C-1: 111.1, C- 151.5, C-7: 169.7, C-8: 194.0, C-9: 10.7, C-10:
2: 159.7, C-3: 98.0, C-4: 164.1, C-5: 107.0, C-6: 18.8, C-1': 116.2, C-2': 159.0, C-3': 111.9, C-4':
141.7, C-7: 174.3, C-1': 119.0, C-2': 149.7, C-3': 150.1, C-5': 120.5, C-6': 137.6, C-7': 172.1, C-8':
141.7, C-4': 144.2, C-5': 111.1, C-6': 127.9 9.7, C-9': 19.2, C-lO': 2004, 7-COOMe: 52.3
MS, m/z 198 (1 %),180 (3), 167 (2),166 (16),165 MS, m/z 402 (M+,6%), 210 (97), 178 (100), 164
(4),153 (12), 152 (60),151 (15), 149 (4), 139 (12), (50), 150 (92), 136 (16)
138 (60),137 (20),135 (6), 124 (9),123 (42), 122 Deriv: Pentaacetylpseudocyphellarin A, plates,
(21), 121 (24), 109 (42), 108 (36), 107 (39), 95 mp 198-200C, from pseudocyphellarin A with
(24), 94 (18), 92 (18),45 (18), 44 (100) Ac 20-H2S0 4
StL: Evernia prunastri (J,...) Ach. StL: Pseudocyphellaria vaccina Malme
Lit: Nicollier 1979 TLC: A: 75, B: 67, B': 74, C: 80, P: 66
HPLC: Rr 44
Lit: Huneck 1984a; lix and Lajide 1984b;
Pulgarin et al. 1985b
3.16 Depsides 295
Pseudocyphellarin B Needles (acetone), mp 220-221 c

React: N aOCI red
CZIH140S (404.40) lH-NMR (CDCI3 ): 2.12, 2.23, 2.59 (3x3H,3xs,
3xMe-), 6.36 (2H,d,-CHOH-9'), 6.98, 7.15
(2xlH,2xs,H-5,H-5'), 11.02, 11.44 (2xlH,2xs,
Me*Me co_o*Me OH 2x-OH)
MS, m/z 218 (S%), 165 (23), 164 (22), 138 (23),
HO OH Me COOMe
137 (15), 136 (22), 55 (100)
CH 20H Me StL: Ramalina americana Hale
8 TLC: RF A: 0.09, C: 0.06, G: 0.18
Lit: Griffin 1993
Needles (acetone), mp 168-169C (dec.)
React: FeCl3 (EtOH) blue-violet, NaOCI red
UV (MeOH): 226 (4.30), 275 (4.25), 318 (3.93); Ramalinolic acid (Ramalinolsaure)
MeOH + NaOH: 228 (4.30), 245 (4.20), 322nm C13H1SOS (432.45)
(4.41)
3"
IR (KBr): 740,776,804,890,966,990, 1002, 1070,
~
1092, 1110, 1170, 1240, 1260, 1318, 1440, 1578, Mel" OH
1604, 1640, 2960, 3250, 3550 cm- 1
CO-O
IH-NMR (l00MHz,CDCI3 -DMSO-d6 ): 2.02 (6H,
s,2xMe-), 2.11, 2.35, 2.57 (3x3H,3xs,3xMe-), MeO 5 3 OH HO
3.92 (3H,s,-COOMe), 4.89 (2H,s,-CH10H-8),
3.13 (IH,bs,-OH), 10.33 (2H,bs,2x-OH), 11.33
(IH,s,-OH)
MS, m/z 210, 178, ISO 5111
Deriv: Tetraacetylpseudocyphellarin B, mp 145- Prisms (benzene), mp 163-164, 169-170C
146C, from pseudocyphellarin B with Ac 20- (needles, toluene-cyclohexane)
H 2 S04 React: NaOCI red, FeCl3 purple, alcoholic K 1C0 3
StL: Pseudocyphellaria vaccina Malme purple
TLC: A: 55, B': 54, C: 48, E: 32 lH-NMR (60MHz,CDCI3-DMSO-d6 ): 0.93 (6H,
HPLC: RI 30 bt,Me-3",Me-5 111 ) , 1.27-1.89 (8H,m,4x-CH1-),
Lit: Huneck 1984a; Elix and Lajide 1984b; 2.78-3.09 (4H,m,-CH1-l",-CH1-l l11 ), 3.81 (3H"
Pulgarin et al. 1985b s,-OMe), 6.39 (3H,bs,H-3,H-5,H-S'), 7.19, 9.63,
11.20 (4H,2xbs,lxs,3x-OH,-COOH)
Ramalinaic acid (Ramalinasaure) MS, m/z 240 (2%),222 (II), 211 (5),210 (33), 197
(S), 196 (34), 194 (7),193 (45), 192 (100), 177 (6),
ClsH160S (360.31) 166 (IS), 165 (7), 164 (21) 153 (10), 151 (6), 149
*
(7),140 (55), 139 (90), 138 (21), 136 (6), 135 (34),
Me CO-O$"'" 0: 131 (7), 122 (6), 121 (6),107 (8), 105 (17),94 (S),
92 (6),91 (16), 79 (8), 78 (7), 77 (15), 71 (9),65
(9),61 (13),53 (6),45 (7),44 (6), 41 (8)
HO OH 5 Deriv: Methyl tri-O-methylramalinolate, prisms
Me H9, 0 (EtOH), mp 75C, from ramalinolic acid with
OH CH1N1
StL: Ramalina calicalis (1.) Fr., Ramalina para-Scrobiculin

nervulosa (Mull.Arg.) Abb.
C22 H 26 0 S (418.43)
TLC: A: 44, B': 57, C: 43
MC: Fig. 33C
Lit: C.F. Culberson 1969; Elix and Norfolk 1975a
meta-Scrobiculin
t
3/1 Me
Me
Deriv: Triacetyl-para-scrobiculin, clustered
il OH
needles (CH 2 Clz-n-pentane), mp 103-107C
5 CO-O~OOMe IH-NMR (CDCI3 ): 0.95, 0.97 (2x3H,2xt,J=7.3Hz,
\111 Me-3",Me-3"'), 1.50-1.75 (4H,m,2x-CH z-), 2.21
MeO 3 OH HO 5' (6H,s,2x-OAc), 2.27 (3H,s,-OAc), 2.65, 2.84
Me (2X2H,2xt,J=7.6Hz,-CHz-l",-CH z-l"'), 3.75,
3'"
3.83 (2x3H,2xs,-OMe,-COOMe), 6.51, 6.73 (2H,
2xd,J=1.8Hz,H-3,H-5), 7.08 (1H,s,H-5')
Crystals (benzene-n-hexane), mp 135.5-136C
MS, m/z 352 (1.5%),321 (3),310 (6), 282 (2), 279
React: KOH bright yellow, KOH + NaOCI red,
(3),268 (48), 240 (1),236 (9),226 (36), 194 (100),
NaOCI red
193 (15), 179 (2), 165 (8)
UV (EtOH): 217.5 (4.69), 265 (4.51), 302.5nm
StL: Lobaria scrobiculata (Scop.) DC.
(4.13)
TLC: RF 0.72 (toluene with 15% AcOH)
IR (Nujol): 715, 770, 786, 795, 806, 845, 855, 952,
HPLC: R] 31
980, 1020, 1045, 1090, ll15, ll65, ll90, 1250,
Lit: Elix and Gaul 1986
1270, 1330, 1370, 1430, 147~ 1565, 1625, 1650,
2900, 3300 cm- 1
IH-NMR (CDCI3 ): 0.87-1.05 (6H,m,Me-3",Me- Sekikaic acid (Sekikasaure)
3"'), 1.36-1.91 (4H,m,2x-CH 2 -), 2.85-3.01 (4H,
bt,-CH z-l",-CH2-1"'), 3.83, 3.96 (2x3H,2xs,- CZZHZ60S (418.43)
OMe,-COOMe), 6.39 (2H,s,H-3,H-5), 6.44 (1H,
s,H-5'), 10.20, 1l.40, 12.02 (3xIH,3xbs,3x-OH)
MS, m/z 418 (M+,O.4%), 226 (18), 195 (15), 194
(100), 193 (13), 179 (ll), 165 (25), 137 (15)
Deriv: Triacetyl-meta-strobiculin, mp 130.5-
131C (MeOH-HzO), from meta-scrobiculin
with Ac 2 0-H zS0 4 on heating on a steam bath for
9 h and held at 70C for 2 days
3'"
StL: Lobaria scrobiculata (Scop.) DC.
TLC: A: 64, B: 55, B': 54, C: 49, E: 39 Prisms (benzene), mp ISO-151C
HPLC: R] 29 React: FeCl3 violet
MC: Fig. 33D UV (MeOH): 219 (4.79), 263 (4.43), 303nm
Lit: C.F. Culberson 1969; Elix and Norfolk 1975a (4.09)
3.16 Depsides 297
IR (KBr): 780, 810, 840, 1040, 1090, 1130, 1155, Needles or plates (benzene), mp 137, 141C
1200, 1225, 1250, 1280, 1320, 1345, 1420, 1460, (CC14 )
1510, 1570,1610, 1630,2950, 3450 cm-l React: FeC13 violet
IH-NMR (200MHz,acetone-d6 ): 0.92 (3H,t,- UV (MeOH): 213 (4.73), 269 (4.37), 304nm
Me), 0.99 (3H,t,-Me), 1.66 (2H,q,-CH 2-), 1.76 (4.15)
(2H,q,-CH 2-), 2.99, 3.02 (2X2H,2xt,-CH2-1",- IR (KBr): 690, 745, 790, 850, 955, 1040, 1070,
CH 2-1"'), 3.85, 3.92 (2x3H,2xs,2x-OMe), 6.38, 1140, 1156, 1200, 1232, 1315, 1360, 1415, 1445,
6.45 (2H,2xd,J=2Hz,H-3, H-5), 6.69 (1H,s,H- 1465, 1570, 1600, 1645, 2900,2950, 3500cm- J
5'), 11.04 (1H,bs,-OH), 12.30 (2H,bs,2x-OH) IH-NMR (200MHz,CDC13-acetone-d6 ): 0.88 (3H,
13C-NMR (25.05 MHz, acetone-d6 ): C-l: 105.2, bt,Me-7"), 1.20-1.54 (1 OH,m,5x-CH 2- ) , 2.67
C-2: 165.9, C-3: 99.7, C-4: 165.3, C-5: 111.4, C- (3H,s,Me-8), 2.90-3.22 (2H,m,-CH z-l"), 3.88
6: 149.0, C-7: 169.3, C-l": 39.2, C-2": 26.0, C-3": (3H,s,-OMe), 6.46 (2H,s,H-3,H-5), 6.78 (2H,s,
14.6, C-4-0Me: 56.5, C-l': 106.9, C-2': 157.3, H-3',H-5'), 11.50 (IH,bs,-OH)
C-3': 125.6, C-4': 156.4, C-5': 106.9, C-6': 146.8, MS, m/z 270 (0.02%), 208 (16), 138 (36), 137
C-7': 173.7, C-l"': 39.2, C-2"': 25.7, C-3"': 14.5, (17), 124 (100), 123 (23), 109 (10), 108 (5), 107
C-4'-OMe: 55.8 (12)
MS, m/z 418 (M+,12%), 374 (30), 226 (20), 225 Deriv: Diacetylsphaerophorin, needles (MeOH-
(100), 209 (50),208 (10), 193 (55), 192 (70), 181 H 2 0), mp 133-134C, from sphaerophorin with
(50), 165 (53) AC zO-H zS0 4
Deriv: Diacetylsekikaic acid, mp 162-163C, StL: Sphaerophorus fragilis (L.) Pers.
from sekikaic acid with ACzO-H zS04 TLC: A: 45, B: 76, B': 74, C: 55
StL: Ramalina boulhautiana Mah. et Gillet HPLC: RJ 46
TLC: A: 45, B: 57, B': 57, C: 51 MC: Fig. 34C,D
HPLC: RJ 28 Lit: C.F. Culberson 1969; Elix and Wardlaw 1987
MC: Figs. 33C; 34A,B
Lit: C.F. Culberson 1969; Elix and Norfolk 1975a;
Squamatic acid (Squamatsaure)
Sundholm and Huneck 1981
Cl9HlS09 (390.33)
*
Sphaerophorin
eo-o*,
9 8'
Me 7 Me
CZ3Hzs07 (416.45)
5 1 OH
i(co-o
8 l' 7'
MeO OH 5' eOOH
OH 8 eOOH 9' Me
Mea 5 3 OH 5' Prisms (acetone), mp 228-229C (dec.)

React: FeC13 purple
UV (MeOH): 214,248, 312nm
IR (KBr): 690, 730, 760, 810, 820, 895, 960, 1002,
1055, 1095, 1120, 1172, 1196, 1250, 1410, 1450,
1500, 1580, 1615, 1680, 1728, 3000, 3280,
Me 3500 cm-l
7/1
IH-NMR (500 MHz, DMSO-d6 ): 2.03 (3H,s,Me-
8'),2.47 (6H,s,Me-9,Me-9'), 3.87 (3H,s,MeO-4),
6.63 (1H,s,H-5), 6.64 (1H,s,H-5'), 12.7 (2H,bs, IR (Nujol): 1145, 1165, 1195, 1215, 1245, 1537,
2xHO-) 1620, 1650, 1675,2500-2800, 3060cm-1
13C-NMR (75.5 MHz, DMSO-d6 ): C-1: 11l.4., C- IH-NMR (60MHz,CDCI3): 0.95 (6H,t,Me-3",
2: 159.9, C-3: 104.7, C-4: 160.B, C-5: 105.5, C-6: Me-5 111 ), 1.45 (BH,m,4x-CH 2 - ) , 3.00 (4H,m,-
143.7, C-7: 165.B, C-B: 170.2, C-9: 21.1, C-4- CH2-1",-CH 2-1 111 ), 3.B5 (3H,s,-OMe), 6.43 (2H,
OMe: 56.3, C-1': 11l.9", C-2': 16l.3, C-3': 115.B, s,H-3',H-5'), 6.66-6.B7 (2H,m,H-3,H-5), 1l.20
C-4': 152.0, C-5': 115.B, C-6': 13B.9, C-7': 173.1, (2H,s,2x-OH)
C-B': 9.0, C-9': 22.B. Values marked with a may MS, m/z 224 (23%), 210 (27), 206 (44), 193 (14),
be exchanged 192 (100), 178 (21), 177 (13), 16B (39), 164 (44),
MS, m/z 390 (M+,0.04%), 346 (O.B), 302 (2), 226 163 (1B), 150 (60),135 (34), 122 (12),121 (10),77
(7),209 (4), 20B (B), 191 (B), 190 (11), 1B3 (5), 1B2 (13),69 (19), 65 (12)
(40), 165 (37), 164 (BB), 163 (5), 13B (21), 137 Deriv: Methyl stenosporate, mp 35-36 DC (n-
(13),136 (64), 135 (9), 123 (5), 121 (27), 110 (9), hexane), from stenosporic acid with CH2N 2 at
109 (13), lOB (13),92 (7),91 (15), BO (6),79 (16), ODC in 30s
7B (11),77 (19),69 (B), 67 (11),66 (9),65 (19),63 StL: Ramalina stenospora Miill.Arg.
(B), 55 (10), 53 (20), 52 (10), 51 (19), 50 (10),45 TLC: A: 44, B: 73, B': 72, C: 52
(7),44 (100), 43 (19),41 (11) HPLC: RI 40
Deriv: Dimethyl squamatate, prisms (acetone), Lit: c.P. Culberson 1970b
mp 183 DC, from squamatic acid with CH 2N2 at
ODC in 1 min
StL: Cladonia squamosa (Scop.) Hoffm. Subconfluentic acid (Subconfluentinsaure)
TLC: A: 13, B: 25, B': 23, C: 2B, G: 39 C26H320S (472.52)
HPLC: RI 22
MC: Fig. 35A
Lit: C.F. Culberson 1969; Elix and Norfolk
1975b, Huneck et al. 1996
Stenosporic acid (Stenosporsaure)

C23 H 2S 0 7 (416.45) eo -0 "C(. 0 ME'
3" OH ~ COOH
Me
MeO 5
~" eo-o
OH 5'
3'
OH
eOOH
ME' or
Me
eo-o o ME'
Me
Sill
OH eOOH
Needles (EtOH-H 20), mp 112-113 DC

UV (EtOH): 215.5 (4.64),270.5 (4.27), 307.5nm
(4.06)
3.16 Depsides 299
Physical data unknown, only micro chemically Needles (EtOAc-n-pentane), mp 156-157C

identified React: NaOCI red
StL: Pseudobaeomyces pachycarpa (Miill.Arg.) IH-NMR (acetone-d6 ): 1.05-1.11 (6H,m,Me-
Sato 3",Me-5 111 ), 1.72-1.88 (8H,m,4x-CH 2-), 2.87-
TLC:A:45, B:43, C:48 2.93, 3.04-3.09 (2x2H,2xm,-CH 2-1",-CH 2-1/11),
Lit: C.F. Culberson et al. 1987 3.98,4.05 (2x3H,2xs,2x-OMe), 6.60 (lH,s,H-5'),
6.67, 6.70 (2x1H,2xd,J=2.1Hz, H-3,H-5)
Subdivaricatic acid (Subdivaricatsaure) MS, m/z 224 (8%), 208 (12),207 (100), 191 (19),
139 (29)
Cl9H2007 (360.35) StL: Cladonia merochlorophaea Asah.
8 TLC: A: 44, B': 47, C: 62
h~CO-O~3' OH
HPLC: R] 19
Lit: C.F. Culberson et al. 1985; Elix et al. 1993a
MeO~OH eOOH 5' rt
Subpaludosic acid (Subpaludossaure)

1 2"
Me C21H 240 S (404.40)

3'/
3"
Crystals (EtOAc-n-pentane), mp 153-154C Me
IH-NMR (acetone-d6 ): 1.09 (3H,t,J=7.3Hz,Me-
3"), 1.79 (2H,q,-CH 2-2"), 2.75 (3H,s,Me-8),
3.12-3.17) (2H,m,-CH 2-1"), 3.24 (1H,bs,-OH), 5~1' CO-0*foH ~OOH
3.99 (3H,s,-OMe), 6.52, 6.58 (2x1H,2xd,J=
2.6Hz,H-3',H-5'), 6.87, 6.90 (2x1H,2xd,J=2.3H, HO~3 OMe HO
5'
1
2'"
H-3,H-5) Me
MS, m/z 196 (23%), 182 (31),178 (88), 164 (100), 3 111
152 (34), 150 (28), 136 (51), 121 (84)
Pale cream rods (EtOAc-n-pentane), mp 181-
182C
TLC: RF A: 0.38, B: 0.65, C: 0.49
React: NaOCI red
Lit: C.F. Culberson et al. 1990a; Elix et al. 1993a
IH-NMR (acetone-d6 ): 1.06, 1.09 (2x3H,2xt,J=
7.4Hz,Me-3",Me-3 111 ), 1.40 (lH,s,-OH), 1.69-,
Submerochlorophaeic acid 1.84 (4H,m,-CH 2 -2",-CH 2-2 111 ), 2.82-2.87, 3.04-
(Submerochlorophaesaure) 3.09 (2x2H,2xm,-CH 2-1",-CH z-1 111 ), 4.01 (3H,
CZZHZ6 0 S (418.43) s,-OMe), 6.56,6.60 (2x1H,2xd,J=2.1Hz,H-3,H-
5),6.59 (lH,s,H-5')
1(
3" MS, m/z 193 (100%), 177 (7),165 (7), 149 (2), 139
Me" (16), 121 (7)
OH
1" StL: Ramalina paludosa B. Moore
eo-o TLC: A: 29, B': 37, C: 29
Lit: C.F: Culberson et aI. 1985; Elix et al. 1993a
MeO 5 OMe HO
3
Subsekikaic acid (Subsekikasaure) MS, m/z 224 (7%), 206 (14), 182 (30), 164 (78),
150 (27), 138 (49), 124 (100)
CZO H 22 0 g (390.38)
StL: Dimelaena thysanota (Tuck.) Hale et
8 W.Culb.
TLC: A: 50, B': 67, C: 50
M.o~::~:~~OOH
~ 3
Me
Superconfluentic acid (Superconfiuentinsaure)
3/1 C3zH440g (556.67)
Plates (EtOAc-n-pentane), mp lS9-160C Me

lH-NMR (acetone-d6 ): 1.07 (3H,t,J=7.4Hz,Me-
3"), 1.73-1.80 (2H,m,-CH z-2"), 2.73 (3H,s,
Me-8), 2.92 (1H,bs,-OH), 3.10-3.17 (2H,m,
-CH z-1"), 3.95, 4.01 (2x3H,2xs,2x-OMe), 6.48,
6.55 (2X1H,2xd,J=2.7Hz, H-3,H-S), 6.77 (1H,s,
H-S'), 7.44 (1H,s,-OH) Co-o
MS, m/z 254 (2%), 208 (30), 182 (53), 164 (85),
153 (100), 136 (68), 121 (45) MeO OH
TLC: RF A: 0.44, B: 0.53, C: 0.50
Lit: C.F. Culberson et al. 1990a; Elix et al. 1993a
Subsphaeric acid (Subsphaersaure)

C21 H24 0 7 (388.40) Physical data unknown, only micro chemically
identified
8 StL: Pseudobaeomyces pachycarpa (Miill.Arg.)
Me Sato
~
3'
5 CO-O --......-......_'-'" OH TLC:A: 53, B:48, C: 63
Lit: C.F. Culberson et al. 1987
MeO OH 5'
3
Superplanaic acid (Superplanasaure)
C31 H 44 0 7 (528.66)
Crystals (EtOAc-n-pentane), mp 120C

lH-NMR (CDCI3): 0.90 (3H,t,Me-S"), 1.14-1.82
(6H,m,3x-CH z-), 2.63 (3H,s,Me-8), 2.86-3.09
(2H,bt,-CH z-1"), 3.82 (3H,s,-OMe), 6.38 (2H,s,
H-3,H-S), 6.66, 6.76 (2x1H,2xd,J=2.SHz,H-3',
H-S'), 11.30 (2H,bs,-OH,-COOH)
3.16 Depsides 301
UV (MeOH): 218 (4.33),260 (4.08), S 285 (3.88),

313nm (3.60)
IR (KBr): 665, 684, 720, 762, 820, 870, 958, 970,
1010, 1045, 1058, 1100, 1120, 1175, 1195, 1230,
1250, 1380, 1415, 1455, 1580, 1630, 1740, 2600,
2700, 3000, 3300 cm- 1
1 CO-O OMf.> 13C-NMR (25.05MHz,DMSO-d6): C-l: 104.1, C-
2: 165.9, C-3: 105.6, C-4: 161.0, C-5: 105.6, C-6:
Me-O
3
oMe- eOOH 144.8., C-7: 164.1, C-8: 170.5b , C-9: 21.5, C-4-
OMe: 56.4, C-l': 111.8, C-2': 160.6, C-3': 108.5,
C-4': 157.1, C-5': 129.4, C-6': 143.6a , C-7':
172.5\ C-8: 194.0, C-9': 15.9 (values marked
with a and b may be exchanged)
MS, m/z 376 (0.25%),332 (0.4),226 (6),209 (15),
208 (6), 192 (5), 191 (43), 190 (9), 182 (16), 169
(7), 168 (67), 167 (40), 166 (24), 165 (68), 164
Crystals (cyclohexane-EtOAc), mp 108 ac
(53),150 (5),139 (6), 138 (13),137 (5), 136 (20),
IH-NMR (CDC1 3 ): 0.86, 0.88 (2x3H,2xbt,J=
122 (16), 121 (24), 109 (5),94 (5), 93 (8), 77 (5),
6.9Hz,Me-7",Me-7"'), 1.20-1.66 (10H,m,-CH 2-
69 (6),67 (5),66 (7),65 (10),53 (11),51 (7),44
2" -6",-CHz-2'" -6"'), 2.70 (2H,t,J=7.9Hz,-CH 2-
(100),43 (9)
1"), 2.78 (2H,t,J=7.8Hz,-CH 2-1"'), 3.85, 3.88,
Deriv: Diemethyl thamnolate, yellowish prisms
3.91 (3x3H,3xs,3x-OMe), 6.38, 6.41 (2xlH,
(benzene or EtOH), mp 158 ac, from thamnolic
2xd,J=2.2Hz,H-3,H-5), 6.73, 6.76 (2xlH,2xd,J=
acid with CHzN 2 at 0 ac in 30 s
2Hz,H-3',H-5')
StL: Thamnolia vermicularis (Sw.) Ach. ex
MS, m/z 264 (17%), 263 (100)
Schaer.
StL: Lecanora planaica Lumbsch
TLC: A: 3, B: 25, B': 21, C: 13
TLC: RF A: 0.53, B: 0.47, C: 0.60
HPLC: RJ 18
HPLC: RJ 0.55
MC: Pig. 35C,D
Lit: c.P. Culberson 1969; Elix and Norfolk 1975c;
Sundholm and Huneck 1981
Thamnolic acid (Thamnolsaure)
Wrightiin
'#
Cl9Hl60n (420.32)
C1s H 17 Cl0 7 (380.77)
#
9 9'
Mf.> Mf.> 8
5
1 to-o 5'
6'
7'
1'< eOOH Me
6 1
7 '
CO-O 4' 3 2' OH
Mf.>O 4 3
2
OH HO 4' 3'
2'
OH
Me-O 4 3
2
OH
Y'(,7'
5 ~COOMe
eOOH CHO
8 8' Cl Me
8'
Pale yellow needles (acetone or dioxane), mp Crystals, mp 216.5 ac
223 ac (dec.) IH-NMR (CDC13 ): 2.58 (3H,dd,J=0.6Hz,Me-),
React: K yellow, PD orange 2.68 (3H,d,J=0.7Hz,Me-), 3.98 (6H,s,-OMe,-
302 3 Data of Lichen Substances <
COOMe), 6.60 (1H,d,J=0.7a.2.5Hz,H-5), 6.70 2-0-Acetyltenuiorin

(2H,d,J=2.5a.0.6Hz,H-3',H-5'), 11.47, 11.53
C2sH2601l (538.39)
(2xlH,2xs,2x-OH)
13C-NMR (DMSO-d6): C-l: 118.8, C-2: 154.3, C- Me Me
3: 106.7, C-4: 157.3, C-5: 106.4, C-6: 137.8", C-7: ~co-o OH ~COOMe
166.4, C-8: 19.39, C-4-0Me: 56.35, C-l': 111.87,
C-2': 156.1, C-3': 107.0, C-4': 151.3, C-5': 113.9,
C-6': 138,0', C-7': 167.8, C-8': 21.18,' 7'-
"'O~OA< ~CO-OAJl-.OH
Me
COOMe: 51.84 (values marked with a may be
exchanged) Crystals (benzene-cyclohexane), mp 203-205 ac
Deriv: Di-O-methylwrightiin, mp 109-111 ac, UV (CHCI3): 268 (3.92), 307.5 nm (3.60)
from wrightiin with MeJ-K2C03 IR (Nujol): 1671, 1760 cm-1
StL: Erioderma wrightii Tuck. lH-NMR (DMSO-d6 ): 1.98 (3H,s,-OAc), 2.45,
TLC: A: 70, B': 55, C: 74, E: 42 2.50, 2.56 (3x3H,3xs,3x-Me), 3.90, 3.96 (2x3H,
HPLC: R, 29 2xs,-OMe,-COOMe), 6.20-6.30 (4H,m,arom.-
Lit: Maass and Hanson 1986; Elix et al. 1988 H), 6.65 (2H,d,J=3Hz,arom.-H), 11.10, 11.59
(2x1H, 2xbs,2x-OH)
3.16.2 MS, mlz 235 (2%),224 (1), 221 (1),207 (16), 193
Tri- and Tetra-Depsides
(5), 182 (2), 165 (35), 150 (1), 138 (8),86 (3), 84
(9),68 (80),66 (100),57 (4), 50 (5),48 (5), 46 (8),
5-0-Acetyl-4-0-methylhiascic acid 43 (8)
(5-0-Acetyl-4-0-methylhiascinsaure) StL: Pseudocyphellaria neglecta (Miill.Arg.)
Magn.
C27H24012 (540.46) TLC: RF A: 0.63, B: 0.53, C: 0.39
8 SH Lit: Bryan and Elix 1976
Me Me
ACO~tO-O" OH ~COOH Aphthosin
Mea~3 aH 5 cOo-aMaH
3/1
C34H30013 (646.58)
Lt"
Me
8' M~ M~
Plates (acetone-n-pentane), mp 165-16rc .J--vcoo OH eoo OH
lH-NMR (acetone-d6 ): 2.30 (3H,s,AcO-5), 2.44 M~O ~

OH ~co.o I
OH ~COOM~ 1m
(3H,s,Me-8), 2.67 (6H,s,Me-8',Me-8"), 3.90 M~ M~
(3H,s,MeO-4), 6.58 (1H,s,H-3), 6.71, 6.76,

6.90, 6.91 (4x1H,4xd,J=2.0Hz,H-3',H-5',H-3", Powder, mp 300 ac (dec.), soluble with difficulty
H-S") in most organic solvents
MS, m/z 330(0.1%), 304 (0.1), 286 (0.2), 256 IR (KBr): 1250, 1580, 1610, 1670, 3420cm- 1
(0.5),223 (5), 198 (1), 193 (2), 180 (15), 168 (2), lH-NMR (60MHz,pyridine-ds): 2.48, 2.65, 2.81
154 (69), 151 (25), 150 (12), 139 (31), 124 (58), (12H,3xs,4xMe-), 3.75, 3.80 (6H,2xs,MeO-,
123 (24),43 (100) MeOCO-)
StL: Koerberiella wimmeriana (K6rb.) B. Stein MS, m/z 346 (0.4%), 332 (2), 182 (40), 165 (17),
TLC: RF A: 0.30, B: 0.34, C: 0.45 164 (44), 151 (31), 150 (100), 136 (15), 124 (8),
Lit: Elix et al. 1991a 123 (8), 122 (43), 121 (13),95 (5),94 (15), 93 (10),
3.16 Depsides 303
77 (8),69 (ll), 67 (ll), 67 (6), 66 (10), 57 (7), 55 HPLC: R J 19

(7), 53 (7), 51 (7) Lit: Huneck et al. 1993c
TLC: B': 1
2,4-Di-O-methylgyrophoric acid
Lit: Bachelor and King 1970; Bryan et al. 1976
(2,4-Di-0-methylgyrophorsaure)
CZ6Hz4010 (496.45)
Crustinic acid (Crustinsa ure)
CZ4HzoOll (484.40) a a"
Me Me
~CO-O~OH ~COOH
it
8
Me 7' II
5 ' co-0;yc3 OH H O 3 OH Mea 3 OMe ) /"eo-o 5" OH
HO OH 5' " CO-O ," eOOH Me

8'
3 7' 7'/
Me Me
8' aU Needles (acetone), mp 169-173C
UV (EtOH): 225 (4.29),255 (4.36), 295nm (4.03)
Needles (MeOH-HzO), mp 178-180C (dec.) IR (Nujol): 1680 cm-1
React: N aOCI red IH-NMR (acetone-d6 ): 2.42, 2.64, 2.70 (3x3H,
UV (MeOH): 226 (4.19),263 (4.26),300 (4.08), S 3xs,Me-8,Me-8',Me-8"), 3.82, 3.88 (2x3H,2xs,
313nm (3.90) 2xMeO-), 6.44 (2H,s,H-3,H-5), 6.64-6.88 (4H,
IR (KBr): 490, 520, 555, 608, 680, 740, 800, 838, m,H-3',H-3",H-5',H-5")
880,965,980,1050,1075,1140,1180,1250,1310, MS, m/z 346 (3%),213 (9), 196 (94),180 (42), 179
1375, 1420, 1440, 1500, 1580, 1620, 1640, 1660, (92), 178 (100), 167 (48), 152 (42), 150 (87), 122
2930,2980, 3180, 3380cm- 1 (50)
IH-NMR (250MHz,acetone-d6 ): 2.52, 2.62, 2.71 StL: Parmelinopsis damaziana (Zahlbr.) Elix
(3x3H,3xs,3xMe-), 6.40 (s,2xarom.H), 6.49 (lH, and Hale
s,H-3"), 6.88, 6.91 (2H,2xd,2xarom.-H), 11.2 TLC: A: 44, B': 35, C: 48
(lH,bs,HO-) HPLC: R J 29
13C_ NMR (62.76 MHz,acetone-d6): 15,68, 23.11, Lit: Elix et al. 1981
24.31 (3xMe-), 101.93, 102.57, 109.61, 113.06,
ll7.86 (5x-CH=), 129.35, 134.25, 134.52, 134.8,
4,2"-Di-O-methylgyrophoric acid
136.2, 140.6, 144.0, 145.0, 155.4, 163.2, 164.4
(4,2"-Di-0-methylgyrophorsaure)
(l3x=C=), 166.8, 170.8, 174 (3x-CO-)
MS, m/z (FAB) 485 (M+H,lbo%), 301 (72), 151 CZ6H24010 (496.45)
(36)
Deriv: Methyl 4"-0-methylcrustinate, needles 8 8"
(CHCI3-MeOH), mp 125-126 c, by methylation
of crustinic acid with CH 2N z in Et 20 at OC in
30s
ko-o;lr.~~ lt~~OH
StL: Umbilicaria crustulosa (Ach.) Frey Mea 3 OH 5/"CO-0 3" OM",
TLC: RF 0.18 (n-hexane: EtzO: HCOOH = 30: 20: Me
6) 8'
Crystals (acetone-n-hexane), mp 140-145C 4,5-di-O-methylhiascic acid with ethereal phe-

UV (MeOH): 227, 258, 298nm nyldiazomethane
IR (KBr): 830,1155, 1190, 1255, 1355, 1405, 1430, StL: Parmelia pseudofatiscens Elix, Parme-
1450, 1640,2840,2920,2985, 3400cm-1 linopsis horrescens (Tayl.) Elix et Hale
IH-NMR (360MHz,DMSO-d6): 2.5 (9H,s,3x- TLC: A: 33, B: 36, B': 41, C: 40
Me-), 3.74 (6H,s,2x-OMe), 6.30, 6.32 (3x2H, HPLC: Rr 31
2xd,J=2Hz,H-3,H-5,H-3',H-5',H-3",H-5"), Lit: Elix and Engkanian 1976b
12.03 (lH,s,HO-)
!3C-NMR (22.11MHz,DMSO-d6): C-1: 106.9, C-
2',2"-Di-O-methyltenuiorin
2: 161.2, C-3: 98.7, C-4: 162.9, C-5: 109.5, C-6:
142.3, C-7: 163.9, C-8: 22.7, C-4-0Me: 54.9, C- CZSHZsO lO (524.50)
1': 110.3, C-2': 153.0, C-3': 105.3, C-4': 161.2, C-
Me Me
5': 110.3, C-6': 142.3, C-7': 162.9, C-8': 22.9,
C-1": 110.8, C-2": 158.0, C-3": 99.7, C-4": 158.0, ffO-OYYOMe ~COOMe
C-5": 108.5, C-6": 139.0, C-7": 172.5, C-8": 22.7,
C-2"-OMe: 54.94
MeO OH /",CO-O~OMe
MS, m/z 182 (75%), 165 (42), 164 (100),150 (15), Me
138 (90), 136 (89), 124 (57), 123 (42), 122 (21), Prisms (acetone-cyclohexane), mp 168-170C
121 (73), 109 (72), 107 (73), 95 (52), 93 (63),79 IH-NMR (CDCI 3 ): 2.37, 2.51, 2.7l (3x3H,3xs,
(42),77 (58), 69 (50),67 (53), 65 (57),51 (7l), 44 3xMe-), 3.90, 3.97 (9H,2xs,2x-OMe,-COOMe),
(73),43 (45) 6.50 (2H,s,H-3,H-5), 6.75-6.88 (4H,m,H-3',H-
StL: Evernia prunastri (1.) Ach. 5',H-3",H-5"), 11.40 (s,HO-)
TLC: A: 45, B': 65, C: 51 MS, m/z 361 (12%), 329 (8), 196 (38), 181 (11),
Lit: Nicollier et al. 1979a 166 (66), 165 (100), 164 (33), 150 (15), 122 (20),
121 (13)
4,5-Di-O-methylhiascic acid StL: Pseudocyphellaria faveolata (Del.) Malme
(4,5-Di-O-methylhiascinsaure) TLC: A: 70, B: 44, B': 29, C: 63, E: 19
HPLC: Rl 31
CZ6Hz4011 (512.45) Lit: Elix and Lajide 1981b
MeO
Me
MenCo-oyyOH
OH /"'CO-O
ff Me
COOH
OH
Gyrophoric acid (Gyrophorsaure)
CZ4HzoOro (468.40)
Me
Crystals (EtOAc-cycloh'exane), mp 168.5-169C
IH-NMR (100MHz,CDCI3-DMSO-d6): 2.61, 2.64,
2.71 (3x3H,3xs,3x-Me), 3.76, 3.94 (2x3H,2xs, HO
Me
ttCO-O;();OH
3 OH O/",CO-O
X:r:Me
5/1
COOH
OH
2x-OMe), 6.48 (1H,s,H-3), 6.60-6.88 (4H,bs,H- Me
3',H-5',H-3",H-5"), 11.16 (2H,bs,2x-OH)
MS, m/z 212 (4%), 194 (100), 178 (28), 168 (5), Ne'edles (acetone), mp 220-225C (dec.)
167 (55), 151 (14), 150 (75), 149 (8) React: NaOCI red, FeCl3 purple
Deriv: Benzyl 4,5-di-O-methylhiascate, plates UV (MeOH): 214 (4.87), 271 (4.44), 305nm
(EtOAc-cyclohexane), mp 129-129.5C, from (4.25)
3.16 Depsides 305
IR (KBr): 700, 740, 800, 840, 870, 900, 985, 1000, (7),55 (9), 53 (15),52 (5), 51 (15),50 (8),44 (90),
1050, 1070, 1140, 1200, 1240, 1310, 1350, 1385, 43 (8), 41 (7)
1450, 1465, 1508, 1610, 1640, 1665, 3050, 3150, Deriv: Methyl hiascate, prisms, mp 144C from
3450cm-1 hiascic acid with CH1N z
IH-NMR (100MHz,DMSO-d6 ): 2.40 (9H,s, StL: Cetrariella delisei (Bory et Schaer.) Karnef.
3xMe-), 6.22(2H,s,H-3,H-5), 6.59-6.68 (4H, et Thell
m,H-3',H-5',H-3",H-5"), 9.97 (1H,bs,HO- or TLC: A: 18, B': 8, C: 12
-COOH), 10.34, 10.40 (2H,2xs,2xHO-) HPLC: Rr 19
MS, m/z 318 (0.4%),274 (5), 169 (5), 168 (50), MC: Fig. 28A
152 (5), 151 (50), 150 (90), 125 (9), 124 (100),123 Lit: C.F. Culberson 1969; Bryan et al. 1976
(54),122 (55), 121 (8),107 (8), 95 (19),94 (25),81
(6), 78 (7), 77 (11), 69 (22),67 (15), 66 (23), 65
3-Hydroxyumbilicaric acid
(15), 63 (5), 62 (5), 55 (13), 53 (16), 52 (6), 51
(3-Hydroxyumbilicarsaure)
(15), 50 (8),44 (55), 43 (12),41 (14)
Deriv: Tetraacetylgyrophoric acid, small C2s H 22 0 11 (498.43)
*
crystals (acetone), mp 228C (dec.), from
gyrophoric acid with Ac 2 0-H2S04
MO CO-OyyOH ~COOH
StL: Lasallia pustulata (1.) Merat
TLC: A: 24, B: 42, B': 42, C: 24, E: 0, F:
HPLC: Rr 25
HO 3 OMe ICO-O OH
MC: Fig. 27A OH Me
Lit: C.F. Culberson 1969; Bryan et al. 1976
Fine needles (EtOAc-n-pentane), mp 186-
187C
Hiascic acid (Hiascinsaure) IH-NMR (acetone-d6 ): 2.37, 2.71, 2.74 (3x3H,
3xs,3xMe-), 4.00 (3H,s,MeO-2), 6.66 (lH,s,
C24H20011 (484.40) H-5), 6.89-6.92 (4H,m,H-3',H-5',H-3",H-5"),
H0iJeco-o;y:,
3'
Me Me 10.74 (4H,s,3xHO-,-COOH)
OH 5"~COOH MS, m/z 198 (3%), 181 (77),168 (42), 150 (100),
137 (9), 122 (47)
HO
3
OH co-oMOH
3
StL: Parmelinopsis bonariensis Adler et Elix
Me TLC: RF A: 0.16, B: 0.26, C: 0.11
HPLC: Rr 16
Small prisms (EtOH), mp 190.5 c (dec.), 200C
(dec.)
React: KOH (trace) red, NaOCI red, FeCl3 blue-
violet, Ba(OHL (H 20) first green, then red 3-Methoxy-2,4-di-O-methylgyrophoric acid
IH-NMR (100 MHz, acetone-d6): 2.57, 2.65, 2.68 (3-Methoxy-2,4-di -0-methylgyrophorsaure)
(3x3H,3xs,3xMe-), 6.39 (1H,s,H-3), 6.80-6.90
C27H26011 (526.48)
*
(4H,m,H-3',H-5',H-3",H-5"), 10.58, 10.68
(2H,bs,HO-,-COOH)
co-o;y:"
Me Me
MS, m/z 318 (1 %),274 (3), 184 (2),168 (37), 166 OH nCOOH
(5), 151 (23), 150 (100), 140 (6), 124 (27), 123
(15), 122 (50), 121 (8), 106 (8), 95 (9),94 (26), 91 MeO OMe 5 CO-O H OH
3
(7), 77 (7), 69 (26), 67 (10), 66 (34), 65 (21), 63 OMe Me
Prisms (acetone-n-hexane), mp 168-170C Me Me

UV (EtOH): 226 (4.26),254 (4.27), 304nm (3.88)
~ca-aY'l(aH ~caaM'
IH-NMR (acetone-d6): 2.36, (3H,s,Me), 2.64, HO~OH icO-O OH
(6H,s,2xMe-), 3.78, 3.86, 3.92 (3x3H,3xs,3x- Me
OMe), 6.76 (5H,s,H-5,H-3',H-5',H-3",H-5")
M5, m/z 482 (2%),376 (2),332 (1),274 (4), 226 Needles (acetone-benzene), mp 224-285, 288C
(12),209 (100),168 (6),151 (5), 150 (4),124 (26)
React: NaOCl red
5tL: Parmelinopsis subfatiscens (Kurok.) Elix UV (MeOH): 216 (4.63), 27l (4.26), 308nm
and Hale (4.04)
TLC: A: 30, B: 33, B': 37, C: 39 IR (KBr): 1616, 1670, 1735cm-1
HPLC: Rr 26 IH-NMR (100MHz,DM50-d6): 2.26, 2.37, 2.38
Lit: Elix and Jayanthi 1981 (3x3H,3xs,3xMe-), 3.82 (3H,s,-COOMe), 6.22,
6.66 (6H,6xarom.-H)
3-Methoxyumbilicaric acid M5, m/z 332 (7%), 183 (5), 182 (45), 168 (5),152
(3-Methoxyumbilicarsaure) (5), 151 (40) 150 (100), 153 (6), 124 (7), 123 (9),
122 (37), 121 (9), 94 (11)
C26H240ll (512.45) Deriv: Methyl tetraacetylgyrophorate, mp 202-
203C (acetone), from methyl gyrophorate with
Me Me Ac 20-pyridine
5tL: Solorina crocea (1.) Ach.
*
CO-O~3' aH nCaaH TLC: A: 52, B: 44, B': 42, C: 43, E: 17
HO OMe 5 CO-O JI OH
HPLC: Rr 30
3 Lit: Ebizuka et al. 1970; Bryan et al. 1976
OMe Me
4-0-Methylgyrophoric acid
Fine needles (EtOAc-n-pentane), mp 170- (4-0-Methylgyrophorsaure)
171C
C2s H 22 0 IO (482.43)
IH-NMR (acetone-d6): 2.33, 2.65, 2.67 (3x3H,
3xs,3xMe-), 3.84, 3.90 (2x3H,2xs,2x-OMe), 6.62
Me Me
(1H,s,H-5), 6.80 (4H,m,H-3',H-5',H-3",H-5"),
10.78 (bs,HO-,-COOH) :((ca-a;y:,
3' aH ::(':(CbOH
M5, m/z 212 (2%), 195 (100), 180 (5), 168 (12),
MeO OH CO-O" OH
150 (58), 122 (55) 3 3
5tU Parmelinopsis bonariensis Adler et Elix Me
TLC: RF A: 0.28, B: 0.32, C: 0.32
HPLC: Rr 21 Crystals (acetone), decomposes slowly above
Lit: Elix et al. 1989c 215C, turning dark yellow and melting at 286-
293C
React: KOH + NaOCl faint pink
Methyl gyrophorate
UV (EtOH): 216 (4.11),270 (4.38), 306nm (4.17)
(Gyrophorsauremethylester)
IR (Nujol): 1580, 1615, 1670, 1685, 3300,
CI9 H 22 0 IO (410.37) 3800cm-1
3.16 Depsides 307
IH-NMR (l00MHz,CDCI3-DMSO-d6 ): 2.48 (3H, MS (negative FAB), m/z 481 (M-H-,50%), 339
s,Me-), 2.54 (6H,s,2xMe-), 3.84 (3H,s,-OMe), (42),325 (60),311 (43),283 (100),255 (72); elec-
6.46 (2H,s,H-3,H-5), 6.70-6.86 (4H,m,H-3',H- tron impact: m/z 348 (50%), 182 (87), 165 (70),
3",H-5',H-5"), 10.77, 10.82 (2xbs,HO-,-COOH) 164 (100), 150 (68)
MS, m/z 332 (1 %), 318 (0.4), 182 (22), 168 (15), StL: Diploschistes gyrophoricus Lumbsch et Elix;
166 (11), 165 (100), 164 (47), 151 (42), 150 (31), Rinodina alba Metzler ex Am.
139 (5), 138 (45), 137 (7), 136 (23), 124 (8), 123 Lit: Elix et al. 1995a
(8), 122 (20), 121 (14), 109 (18), 108 (11), 107
(14), 95 (8), 94 (12), 93 (14), 79 (7), 78 (11), 77 2-0-Methylhiascic acid
(14), 69 (15), 67 (9), 66 (15), 65 (14), 63 (5), 55 (2-0-Methylhiascinsaure)
n
(7),53 (10),52 (6), 51 (13),50 (6), 44 (100), 43
C2s H 22 0 11 (498.43)
(12),41 (8)
StL: Lobaria dissecta (Sw.) Rausch. Me Me
TLC: A: 32, B: 56, B': 50, C: 46
H0Xx:CO-OyyOH COOH
HPLC: RI 34
Lit: C.F. Culberson 1970a; Bryan et al. 1976 HO OMe ICO-O OH
Me
2"-0-Methylgyrophoric acid
(2" -0-Methylgyrophorsaure) Prisms (acetone-cyc1ohexane-toluene), mp
137-139C
C2sH22010 (482.43) UV (EtOH): 222 (4.08),271 (4.09), 307nm (3.93)
Me Me
IH-NMR (acetone-d6 ): 2.32, 2.62, 2.66 (3x3H,
5~CO-0~' 3'2' OH 5,,6" ," eOOH 3xs,3xMe-), 3.84 (3H,s,MeO-), 6.38 (lH,s,H-3),
;U
HO 4 3 OH
5'
6'
"
eo-o 4/1 3/1
6.80 (4H,s,4xarom.-H)
MS, m/z 413 (1 %),383 (2), 196 (2),168 (27),150
Me (44), 124 (100)
StL: Parmelinopsis neodamaziana (Elix et
Crystals (acetone-n-hexane), mp 176-178C Johnston) Elix et Hale
(dec.) TLC: RF A: 0.11, B: 0.20, C: 0.39
React: NaOCl red HPLC: Rj 17
IH-NMR (300MHz,CDCI3 -DMSO-d6 ): 2.41,2.62, Lit: Elix et al. 1989b
2.66 (3x3H,3xs,3x-Me), 3.89 (3H,s,-OMe), 6.33,
6.35 (2x1H,2xd,J=2.2Hz,H-3,H-5), 6.69, 6.78 2' -O-Methylhiascic acid
(2x1H,2xd,J=2.0Hz,H-3",H-5"), 6.72 (2H, (2' -0-Methylhiascinsaure)
s,H-3',H-5'), 10.02 (2H,bs,2"-OH,-COOH),
10.90 (1H,s,HO-4), 11.21 (lH,s,HO-2) C2s H 22 0 11 (498.43)
!3C-NMR (CDCI 3-DMSO-d6 ): 17.03, 18.70,21.43 8 8"
(3x-Me), 54.15 (-OMe), 99.36, 101.69, 106.40, Me 7 Me
3' 7
110.11,113.54,113.70 (6x=CH-), 103.21, 114.97,
~
II
HO , eo-o~' 'OMe 5,,6 ," eOOH
122.00, 135.00, 138.08, 141.23 (C-2,C-4,C-6,C- 5 2 5 ' " 7' 4" 1/
2',C-4',C-6',C-2",C-4",C-6"), 150.04, 151.28, HO 4 3 OH 6' CO-O 3/1 OH
155.48 (C-1,C-1',C-1"), 165.39, 166.80, 167.57 Me
(3x-CO-) al
Prisms (acetone), mp 207-209C 5-0-Methylhiascic acid

React: NaOCl red (5-0-Methylhiascinsaure)
IR (KBr): 795,840, 1250, 1600, 1665, 1720,2880,
C2sH220Jl (498.43)
2920, 3300 cm- 1
IH-NMR (100MHz,DMSO-d6 ): 2.27 (3H,s,Me-
8'), 2.37 (3H,s,Me-8"), 2.43 (3H,s,Me-8), 3.63 Me Me
(3H,s,MeO-2'), 6.38 (1H,s,H-3), 6.56 (1H,d,J=
2.05Hz,H-5'), 6.60 (1H,d,J=2.05Hz,H-5"), 6.66 Meo~co-0;y:3' OH nCOOH
(1H,d,J=2.05Hz,H-3'), 6.69 (1H,d,J=2.05Hz,H-
3"),9.94 (2H,s,HO-4,HO-5), 10.54 (lH,s,HO-2)
HO ~OH
3
5 CO-O
3-
OH
Me
J3C-NMR (25.15MHz,DMSO-d6 ): C-1: 109.53,
C-2: 153.63', C-3: 101.76, C-4: 153.77', C-5:
156.77, C-6: 138.98, C-7: 166.48b , C-8: 21.31 c, C- Prisms (acetone-n-hexane), mp 188-189C
1': 118.13, C-2': 160.03, C-3': 107.16d, C-4': (dec.)
152.21 e, C-5': 114.12 f , C-6': 137.98, C-7': 165.69b, React: NaOCI red, FeCl3 violet
C-8': 19.32c, C-2'-OMe: 59.79, C-1": 118.13, C- IR (Nujol): 1672 cm- 1
2": 140.10, C-3": 107.35d, C-4": 152.03', C-5": IH-NMR (100MHz,acetone-d6 ): 2.40, 2.57, 2.67
114. 15 f , C-6": 138.98, C-7": 170.90, C-8": 13.28C (3x3H,3xs,3xMe-), 3.70 (3H,s,MeO-), 6.38 (1H,
(values marked with a, b, c, d, e and f can be s,H-3), 6.78-6.86 (4H,m,H-3',H-5',H-3",H-5")
exchanged) MS, m/z 348 (1 %),334 (1), 318 (3), 304 (3), 274
MS, m/z 168 (7%), 166 (12), 165 (5),151 (12), 138 (2), 198 (14), 181 (28),180 (27), 169 (5), 168 (50),
(26), 135 (10), 124 (100), 123 (68), 111 (17), 107 165 (18), 152 (10), 151 (84), 150 (100), 139 (10),
(12), 95 (27), 94 (11), 78 (58), 63 (72) 137 (13), 124 (14), 123 (12), 122 (56), 121 (9),94
StL: Catillaria corymbosa (Hue) Lamb (20), 69 (35),67 (11),66 (20), 65 (15)
TLC: A: 12, B': 22, C: 10 Deriv: Methyl 5-0-methylhiascate, mp 162-
Lit: Vinet et al. 1990b 164C (acetone-n-hexane), from 5-0-methyl-
hiascic acid with CH 2N2 in Et2 0 at OC in 2 min
4-0-Methylhiascic acid StL: Parmelinopsis horrescens (Tayl.) Elix and
(4-0-Methylhiascinsaure) Hale, Parmelinopsis minarum (Vain.) Elix et
Hale
C2s H 22 0 Jl (498.43) TLC: A: 21, B: 35, B': 36, C: 29
HPLC: R] 24
Me Me Lit: Elix and Jayanthi 1977
HO~CO-O~OH ~OOH
2-0-Methyltenuiorin
MeO ~ OH ~CO-O OH
C27 H 26 0 JO (510.48)
Me

Me Me
MS, m/z 198, 196, 180 .5~co-0;y:3 OH ~COOM.
StL: Parmelinopsis schindleri (Hale) Elix et Hale
TLC: A: 26, B: 26, B': 19, C: 35 MeO~OMe
3
5 CO-O
3
/I OH
Lit: Elix and Jayanthi 1977; Elix et al. 1991a Me
3.16 Depsides 309
prisms (acetone-cyclohexane), mp 132-133.5C Prisms (acetone-cyclohexane), mp 124-126C

IH-NMR (CDCI3 ): 2.48, 2.64, 2.74 (3x3H, IH-NMR (CDCl3): 2.33, 2.63, 2.71 (3x3H,3xs,
3xs,3xMe-), 3.91, 4.02 (9H,2xs,2x-OMe,lx- 3xMe-), 3.84 (6H,s,2xOMe), 3.92 (3H,s,-OMe),
COOMe), 6.40 (2H,s,H-3,H-5), 6.65-6.90 (4H, 6.38 (2H,s,H-3,H-5), 6.66-6.76 (4H,m,H-3/,H-
m,H-3/,H-5/,H-3",H-5"), 11.15, 11.64 (2xlH, 5/,H-3",H-5"), 11.16, 11.29 (2XIH,2x-OH)
2xs,2x-OH) MS, mlz 331 (2%),314 (4),196 (29), 179 (6), 166
MS, m/z 196 (21%), 182 (50), 179 (100), 150 (11), 165 (100), 164 (31), 151 (11), 150 (11)
(100),122 (60) StL: Pseudocyphellaria Javeolata (Del.) Malme
StL: not yet found in lichens TLC:A:73,B:44,C:66,E:26
TLC: A: 66, B/: 40, C: 62, E: 24 HPLC: RJ 33
HPLC: RJ 33 Lit: Elix and Lajide 1981b
Lit: Elix and Lajide 1981b
Orcinyllecanorate (Lecanorsaureorcinylester)
2/ -O-Methyltenuiorin C23H200S (424.39)
Crystals (acetone-H20), mp 142-144C
0:
C27H26010 (510.48)
Me Me
5
Me
CO-O 3' OH.":((Me
~co-o;yc3' OMe 5,,~cOOMe
MeO OH 5 co-oMoH
HO 3 OH ~CO_05 3" 1 OH
3 3 Me
Me
React: NaOCI red
Prisms (acetone-cyclohexane), mp 144-146C IH-NMR (acetone-d6 ): 2.30, 2.61, 2.67 (3x3H,
IH-NMR (CDCI3): 2.50, 2.67, 2.75 (3x3H,3xs,3x- 3xs,3xMe-), 6.30, 6.38 (2X1H,2xd,]=2Hz,H-3/,
Me), 3.84, 3.95, 4.00 (3x3H,3xs,3x-OMe), 6.41 H-5/), 6.62 (3H,s,H-l",H-3",H-5"), 6.83 (2H,bs,
(2H,s,H-3,H-5), 6.61-6.85 (4H,m,H-3/,H-5/, H-3,H-5)
H-3",H-5"), 11.59, 11.77 (2xlH,2xs,2x-OH) MS, m/z 275 (12%),274 (67), 152 (72), lSI (100),
MS, m/z 347 (7%), 183 (10), 182 (19), 166 (12), 150 (19), 125 (18),124 (92),123 (89), 122 (17), 95
165 (100), 164 (21), 151 (16), 150 (52), 122 (30), (55),77 (34), 69 (63), 67 (55)
121 (18) StL: Punctelia borreri (Sm.) Krog
StL: Pseudocyphellaria Javeolata (Del.) Malme TLC: A: 30, B: 37, B/: 38, C: 20, E: 11
TLC: A: 70, B/: 44, C: 72, E: 31 HPLC: RJ 20
HPLC: RJ 37 Lit: Chester and Elix 1981b
Lit: Elix and Lajide 1981b
Ovoic acid (Ovosaure)
2"-O-Methyltenuiorin C2s H 22 0 11 (482.43)
II '
C27H26010 (510.48) 8
Me Me ~L7Co-ft~Me
~CO-O*OH 5"~COOM' HO 4 3 OH 5'~CO-0
MeO 3 OH 5IcO-O~OMe Me
Me 8'
Needles (MeOH), mp. 178-180C

React: NaOCI red, PeCl3 (EtOH) violet
UV (MeOH): 214 (4.63), 272 (4.19), 302nm UV (MeOH): 207 (4.44), S 216 (4.28),267 (3.90),
(3.95) 307nm (3.63)
IR (KBr): 690, 840, 890, 954, 990, 1038, 1054, IR (KBr): 700, 800, 815, 840, 862, 910, 950, 962,
1090, 1130, 1190, 1240, 1302, 1378, 1412, 1446, 990, 1005, 1042, 1070, 1150, 1200, 1250, 1315,
1486, 1596, 1644, 1740,3000,3200, 3500cm-1 1370, 1422, 1450, 1510, 1580, 1605, 1670, 3000,
IH-NMR (100MHz,acetone-d6): 2.46, 2.63, 2.64 3450cm-1
(3x3H,3xs,3xMe-), 3.96 (3H,s,-OMe), 6.31, IH-NMR (100MHz,DMSO-d6): 2.27, 2.38, 2.42
6.39,6.39,6.41 (2H,d,J=2.7Hz,2xarom.-H), 6.70, (3x3H,3xs,3xMe-), 3.76, 3.82 (2x3H,2xs,-OMe,
6.73,6.75,6.78 (2H,d,J=2.7Hz,2xarom.-H), 6.88, -COOMe), 6.34 (6H,bs,6xarom.-H)
6.90, 7.04, 7.06 (2H,d,J=1.95Hz,2xarom.-H), MS, m/z 346 (0.8%), 332 (4), 183 (5), 182 (50),
10.2, 11.25 (4H,bs,3x-OH,-COOH) 165 (81), 164 (32), 152 (5), 151 (56), 150 (100),
13C-NMR (29.05MHz,acetone-d6): C-1: 104.6, 136 (10),123 (6), 122 (56), 121 (9),95 (5), 94 (20),
C-2: 166.7, C-3: 101.7, C-4: 163.9, C-5: 112.8, 69 (17),67 (8),66 (21),65 (12), 56 (6), 54 (10), 52
C-6: 144.7, C-7: l70.6, C-8: 24.4, C-1': 121.3, C- (9), 41 (7)
2': 158.3, C-3': 104.7, C-4': 153.0, C-5': 116.6, C- Deriv: Triacetyltenuiorin, plates (CHzClz-
6': 138.7, C-7': 165.6, C-8': 19.3, C-2'-OMe: MeOH), mp 199-200C, from tenuiorin with
56.8, C-1": 110.9, C-2": 165.5, C-3": 109.0, C-4": AC zO-H 2 S0 4
155.8, C-5": 117.0, C-6": 144.7, C-7": 173.5, C- StL: Peltigera polydactyla (Neck.) Hoffm.
8": 24.0 TLC: A: 76, B: 58, B': 55, C: 76, E: 25
MS, m/z 182 (16%), 165 (84), 151 (64), 138 (80), HPLC: RI 39
124 (100) MC: Pig. 35B
Deriv: Methyl ovoate, needles (CHCI3-MeOH), Lit: c.P. Culberson 1969; Bryan et al. 1976
mp 158-159C, from ovoic acid with CHzN z in
EtzO at OC in 30 s
2,4,5-Tri-O-methylhiascic acid
StL: Melanelia substygia (Ras.) Essl.
(2,4,5-Tri -0-methylhiascinsaure)
TLC: A: 25, B': 34, C: 23
HPLC: RI 23 C27H26011 (526.48)
ME' ME'
Tenuiorin "'O~CO-0Y(0H ~COOH
ME'O~OME' ,CO-O OH
ME'
Prisms (acetone-cyclohexane-toluene), mp
ME' ME'
173-176C
~CO-0"('l(0H ~COOME' UV (EtOH): 223 (4.33),253 (4.28), 300nm (3.97)
ME'OAJl.. OH ,CO-O~OH IR (Nujol): 1660 cm- 1
ME'
(6H,s,2xMe-), 3.68, 3.90, 3.92 (3x3H,3xs,3x-
OMe), 6.72-6.86 (5H,m,5xarom.-H)
Plates (benzene), mp 178-180C, solidifies and MS, m/z 376 (8%),226 (36),211 (31),209 (100),
then decomposes at 238C 193 (21), 168 (30), 150 (46), J22 (28)
3.16 Depsides 311
StL: Parmelinopsis damaziana (Zahlbr.) Elix et 3.16.3

Hale Benzyldepsides
TLC: A: 40, B: 35, B': 31, C: 38
Lit: Elix et al. 1981 Alectorialic acid (Alectorialsaure)
ClsH1609 (376.31)
Umbilicaric acid (Umbilicarsaure)
C2s H 22 0 lO (482.43)
n *
9 7'
eOOH
Me, to-O-t'H
Me 5 2
eo -0
3' :((Me eOOH
OH" 2 ,
5 HO 4 3 OH 5
HO 5 3 OMe ;YCCO-O 3" OH
CHO OH
Me 8
Plates (EtOH), mp 185-189, 203C (dec.);

needles (EtOH-H 20), mp 185C Needles (EtOH-H 20), mp 176-179C
React: FeCl3 violet React: KOH yellow, NaOCl red, PD yellow, FeCl3
UV (MeOH): 213 (4.93), 257 (4.38), 293nm purple-red
(4.20) UV (MeOH): 219 (4.45), 243 (4.49),263 (4.47),
IR (KBr): 700, 795, 870, 900, 970, 1000, 1040, 335 (3.75); MeOH + NaOH: 219 (4.54), 276
1062, 113-8, 1158, 1182, 1230, 1310, 1340, 1380, (4.48), S 294 (4.41), 390 (3.71); MeOH + AlCl 3:
1420, 1450, 160~ 1670, 1718, 300~ 3100, 227 (4.62), S 256 (4.50), S 310 (4.20), 375nm
3500cm-1 (3.78)
IH-NMR (100MHz,CDCl3 -DMSO-d6 ): 2.36, 2.63, IR (KBr): 740, 770, 800, 820, 840, 900, 930, 980,
2.67 (3x3H,3xs,3xMe-), 3.82 (3H,s,-OMe), 6.32 1120, 1170, 1210, 1250, 1300, 1410, 1450, 1620,
(2H,s,H-3,H-5), 6.55, 6.76 (2xlH,2xd,J=3Hz, 3000, 3450 cm- 1
2xarom.-H), 6.68 (2H,m,2xarom.-H), 8.80 (1H, IH-NMR (60MHz,DMSO-d6): 2.01, 2.37, (2x3H,
bs,-OH or -COO H), 11.05 (1H,bs,-OH) 2xMe-), 5.60 (2H,s,-CH 2-9'), 6.41 (2H,s,H-
MS, m/z 182 (11%), 168 (55), 165 (9), 164 (14), 5,H-5'), 10.30 (1H,s,-CHO-8)
151 (15), 150 (100), 138 (29), 124 (48), 123 (29), 13C-NMR (25.05MHz,DMSO-d 6 ): C-l: 110.2, C-'
122 (59), 121 (10),109 (14), 108 (6),107 (13),106 2: 162.3, C-3: 107.9, C-4: 163.4, C-5: 109.3, C-6:
(5), 95 (12), 94 (27), 77 (10), 69 (24), 67 (13), 66 149.4, C-7: 167.0, C-8: 193.3, C-9: 22.1, C-l':
(26),65 (17),63 (6), 55 (13L 53 (19),52 (7), 51 101.9, C-2': 163.0, C-3': 109.9, C-4': 160.2, C-5':
(17),50 (9),44 (64),43 (13),41 (15) 107.2, C-6': 136.7, C-7': 173.0, C-8': 8.2, C-9':
Deriv: Triacetylumbilicaric acid, needles (ac- 66.0
etone-H 20), mp 197C (dec.), from umbilicaric MS, m/z 332, 179, 150
acid with Ac20-H 1 S0 4 Deriv: Methyl alectorialate, mp 202-~J4 c
StL: Umbilicaria polyphylla (1.) Baumg. (MeOH), from alectorialic acid with CH 1N 2 in
TLC: A: 25, B': 29, C: 18 dioxane-Et 20 at -5C in 1')~:
HPLC: R] 25 StL: Alectoria nigricans (Ach.) Nyl.
MC: Fig. 36C TLC: A: 36, B: 48, B': 50, C: 32, G: 60
Lit: C.F. Culberson 1969; Bryan et al. 1976 HPLC: R] 18
MC: Figs. 16D; 17A,B Needles (dioxane), mp 206-20rc (dec., softens

Lit: Solberg 1967; Persson and Santesson 1970; from 190C)
Sundholm and Huneck 1981; Elix and Jayanthi React: KOH yellow, PD orange, FeCl3 brown,
1987a NaOCI red
Deriv: Methyl barbatolate, needles (AcOH), mp
193C, from barbatolic acid with CHzNz
Alectorialin
StL: Bryoria capillaris (Ach.) Brodo et D.
Cl7Hl607 (332.30) Hawksw.
TLC: A: 9, B: 48, B': 52, C: 26, G: 45
9 HPLC: R[ 16
Me 9' , MC: Fig. 20C
*
CO-O-CH2~1,OH Lit: C.F. Culberson 1969; Elix and Jayanthi 1987a
5' 3
HO OH ~~
Barbatolin
CHO OH
8 Cl7Hl40S (346.28)
#
Needles (cyclohexane-acetone), mp 200-201C 9
(dec.) Me 7 9' 1
React: NaOCI red, PD yellow 6 1 CO-O-CH2:v,l

2' OH
IH-NMR (CDCI3-DMSO-d6): 2.00, 2.46, (2x3H, 2 3/ 8/
2xs,Me-9,Me-8'), 5.20 (2H,s,-CH z-9'), 6.30 HO 4 OH 5' 4/ CHO
(lH,s,H-5), 6.46 (2H,s,H-1',H-5'), 10.34 (lH,s, CHO OH
-CHO-8), 12.00, 12.78 (2x1H,2xs,2xHO-) 8
MS, m/z 332 (M+,20/0), 314, 301, 137 (100)
StL: Alectoria nigricans (Ach.) NyL Needles (CHCI 3-acetone-n-hexane), mp 219-
TLC: A: 37, B': 34, C: 13, E: 10, G: 49 220C (dec.)
HPLC: R[ 13 React: NaOCI red, PD yellow
Lit: Elix and Jayanthi 1987a IH-NMR (CDCI3-DMSO-d6 ): 2.44 (3H,s,Me-9),
5.28 (2H,s,-CH z-9'), 6.36 (lH,s,H-5), 6.48
(2H,s,H-1',H-5'), 10.34 (lH,s-CHO-8)
Barbatolic add (Barbatolsaure) MS, m/z 346 (M+,1000/0), 179 (53), 177, 150 '
ClsHl4010 (390.29) TLC: A: 46, B': 43, C: 30, E: 13, G: 60
StL: Bryoria nadvornikiana (Gyelnik) Brodo et
D. Hawksw.
~CO~O-CH2~OH Lit: Elix and Jayanthi 1987a
HO~OH ~CHO
CHO OH
3.17 Depsidones 313
3.17 IH-NMR (200MHz,CDCl3 -acetone-d6): 1.98 (3H,

Oepsidones s-OAc), 2.23, 2.45 (2x3H,2xs,Me-8,Me-9), 3.86
(3H,s,-OMe), 5.17 (2H,s,-CH z-8'), 6.70 (1H,bs,
a-Acetylconstictic acid H-9'), 6.80 (1H,s,H-5), 8.40, 10.50 (2x1H,2xbs,
(a-Acetylconstictinsaure) 2x-OH)
MS, mlz 430 (M+,l %), 370 (45), 342 (24), 326
C21 H 16 0 11 (444.34) (27), 298 (25), 179 (16), 178 (22)
StL: Xanthoparmelia metastrigosa (Elix) Hale
9 TLC: A: 34, B':14, C: 20, G: 46
Me
sf4;to-o
o
Meo~o a-Acetylsalazinic acid, Galbinic acid
CHO (a-Acetylsalazinsaure, Galbinsaure)
8
CZOH140ll (430.31)
Crystals (acetone-n-pentane), mp > 230 DC
*
(dec.) 9 8'
React: PD orange
IH-NMR (200MHz,CDCl3-acetone-d6): 1.99 (3H,
Me co_:&;CH20~~OMe
s,-OAc), 2.57 (6H,s,2x-Me) 4.00 (3H,s,-OMe),
5.26 (2H,s,-CH z-8'), 6.95 (1H,bs,H-9'), 7.09 HO 0
o
(1H,s,H-5) CHO HO 9' 0
MS, mlz 384 (0.1%), 370 (0.2), 342 (0.5), 326 8
(0.1), 314 (1), 298 (0.4) 286 (0.5), 271 (0.2), 258
(0.5),230 (0.6), 193 (0.6), 191 (0.8) Crystals (EtOAc-n-pentane) which decompose
StL: Menegazzia platytrema (Mull.Arg.) R.Sant. at 260-265 DC without melting; needles (ac-
TLC: A: 16, B': 4, C: 11, G: 23 etone-H 2 0 or MeOH-H 20), mp 205-20rC
Lit: Elix et al. 1987b React: KOH yellow ---') red-brown, PD yellow,
FeC13 (EtOH) wine red
UV (MeOH): 241 (4.46),321 nm (3.93)
a-Acetylhypoconstictic acid IR (KBr): 790, 806, 840, 860,900,960,1020, 1090,
(a-Acetylhypoconstictinsaure) 1140, 1160, 1200, 1250, 1290, 137~ 139~ 145~
C21HlSOlO (430.35) 1570, 1648, 1732, 3490cm-1
IH-NMR (60MHz,DMSO-d6): 2.00 (3H,s,-OAc),

2.47 (3H,s,Me-9), 3.55 (3H,bs,-OH,H zO), 5.15
9 8'
(2H,s,-CH 2-8'), 6.73 (lH,s,H-9'), 6.76 (lH,s,H-
Me co_:&;CH2-~:COMe 5), 10.32 (1H,s,-CHO-8), 11.88 (lH,bs,-OH)
MS, mlz 152 (29%), 151 (32),60 (52),45 (75),44
(100),43 (77)
MeO 0
Deriv: :tIexaacetylsalazinic acid, prisms, mp
Me HO 9' o 176-178 DC from a-acetyl-salazinic acid with
8
AC zO-H zS0 4
Crystals (acetone-n-pentane), mp 220-240DC StL: Myelochroa galbina (Ach.) Elix et Hale, Us-
(dec.) nea undulata Stirt.
HPLC: RJ 9 StL: Alectoria lata (Tayl.) Linds.

MC: Fig. 58D TLC: A: 33, B: 34, B': 31, C: 17
Lit: Asahina and Tukamoto 1934; Elix and HPLC: RI26
Engkanian 1975; Huneck and Schreiber 1976 MC: Figs. 36D; 37A,B
Lit: C.F. Culberson 1969; Elix et al. 1974
a-Alectoronic acid (Alectoronsaure)
Allorhizin
C2sH3209 (512.54)
7" CIsH14Cl206 (397.20)
Me Me
3 o
Needles (CH 2Clc n-hexane), mp 230-232 DC
(dec.)
React: PD yellow
7"1
Me IH-NMR (CDCI 3): 2.26, 2.38, 2.50 (3x3H,3xs,3x-
Me), 3.81 (3H,s,-OMe), 6.20 (1H,bs,-OH), 10.60
Needles (benzene), mp 193 DC; hydrate (MeOH- (1H,s,-CHO)
H 20), mp 120-121 DC, resolidifies at HODC and MS, m/z 398 (M+,12%), 396 (25), 382 (14), 368
melts again at 193 DC (12), 163 (43),361 (100),347 (50),340 (40),322
React: KOH + NaOCI red, FeCl3 violet (12),321 (12),201 (3), 199 (8), 198 (8),196 (10),
UV (MeOH): 211 (4.49),260 (3.94), 310 (3.54) 182 (8), 179 (6), 164 (12), 156 (15)
IR (KBr): 740, 790, 808, 870, 895, 950,1022,1080, StL: Psoroma allorhizum (Nyl.) Hue
1100, 1150, 1210, 1250, 1330, 1360, 1420, 1478, TLC: RF A: 0.57, B: 0.56, C: 0.65
1570, 1608, 1695, 2950, 3300 cm-1 Lit: Elix et al. 1982a
IH-NMR (100MHz,acetone-d6): 0.80-1.05 (6H,
m,Me-7",Me-7111 ) , 1.05-1.85 (12H,m,6x-CH 2-),
2.16 (2H,m,-CH 2-3 111 ), 2.54 (2H,t,-CH 2-3"), 3.10- Argopsin, l' -Chloropannarin
3.90 (2H,bs,-CH2-1 111 ), 4.04 (2H,s,-CH 2-1"), 6.68- (1' -Chlorpannarin)
6.78 (3H,m,H -3,H -5,H -3'), 11.20 (bs,-OH) CIsH14Cl206 (396.20)
MS, m/z494 (12%),468 (IO), 450 (5),371 (6),370
(23),369 (4),352 (1),245 (3)
Deriv: Methyl alectoronate, needles (MeOH),
mp 160 DC, from alectoronic acid with the
CL~CO-O~OM'
equimolar amount of CH 2N 2 at ODC
MS, m/z 526 (M+,2%), 512 (3), 494 (100), 468
HO~o~CI
CHO Me
(20),396 (20),370 (30), 354 (7), 272 (3),248 (5), 8
192 (4), 163 (3), 150 (7),134 (8), 123 (4), 105 (7),
99 (20),81 (6),71 (20),55 (18),45 (40),44 (70), Prisms (CH 2CI2-MeOH), mp 220-221 DC
43 (55) React: PD orange, FeCl3 (EtOE) red
3.17 Depsidones 315
UV (MeOH): 213 (4.24), S 250 (4.04), 310 (3.57), Cetraric acid (Cetrarsaure)
360 nm (3.30)
C2oHlS09 (402.34)
IR (KBr): 700, 730, 762, 808, 880, 1010, 1030,
1090, 1115, 1060, 1220, 1255, 1300, 1355, 1410,
1450,1465,1565, 1640, 1725,2950, 3500cm-1
IH-NMR (60MHz,CDC1 3): 2.33, 2.45, 2.57
~CO-OX~M'
(3x3H,3xs,3x-Me), 3.79 (3H,s,-OMe), 10.77
(1H,s,-CHO)
HO~o~COOH
MS, m/z 400 (M+), 398, 396, 215, 214, 213, 186, CHO Me
185, 184, 158, 15~ 156 Needles (EtOH), mp 240C (dec. from 215C)
Deriv: Triacetylargopsin, mp 225-226C, from React: PD orange
argopsin with Ac 20-H 2S04 StL: not yet found in lichens
StL: Argopsis friesiana MUll.Arg. Lit: Asahina and Yanagita 1933b
TLC: A: 77, B': 73, C: 82, E: 43
HPLC: R[ 43
Lit: Bodo and Molho 1974; Huneck and Lamb Chlorogranulatin (Chlorgranulatin)
1975; Quilhot et al. 1983 C19HIsClOs (406.76)
Me Me
Caloploicin
C17H13C130 s (403.64)
CIWCO-O~OH
HO~o~COOMe
H:*:~:'~
CHO Me
Crystals (after sublimation), mp 202-203C

React: PD yellow
CI Me IR (KBr): 600, 641, 708, 771, 778, 900, 910, 970,
1020, 1030, 1078, 1124, 1165, 1205, 1250-1325,
Needles (benzene), mp 255-256, 260.5C
1648, 1665, 1739, 3350-3570cm- 1
IR (KBr): 690, 735, 780, 806, 870, 894, 996, 1086,
IH-NMR (60MHz,CDC13 ): 2.27 (3H,s,Me-), 2.55
1124, 1180, 1210, 1250, 1342, 1410, 1438, 1462,
(6H,s,2xMe-), 3.93 (3H,s,-COOMe), 10.63 (1H,
1546, 1570, 1696, 1724,3000, 3500cm- 1
s,-CHO-8), 11.35 (lH,s,-OH-2'), 12,73 (1H,
IH-NMR (90MHz,DMSO-d 6): 2.26, 2.41, 2.54
s,HO-4)
(3x3H,3xs,3x-Me), 3.73 (3H,s,-OMe)
MS, m/z 408 (M+,35%), 406 (100), 376 (21), 374
MS, m/z 404 (M+), 402, 367
(55), 348 (29),346 (73), 321 (10),320 (13), 319
Deriv: Acetylcaloploicin, mr 230-231.5 DC, from
(31), 318 (26), 308 (24), 306 (65), 294 (32), 293
caloploicin with Ac20-pyridine
(18), 292 (95), 291 (10), 290 (18), 215 (5), 231
StL: Caloplaca sp. from Japan
(16), 211 (7)
TLC: A: 65, B': 69, C: 58, E: 29
StL: Pseudocyphellaria granulata (Bab.) Malme
HPLC: R,39
Lit: Goh and Wilkins 1979
Lit: Yosioka et al. 1971 a, 1973; Sargent and
Vogel 1976
Chlorolecideoidin (Chlorlecideoidin) HPLC: Rt 5.17min

C I7 H ll CI0 7 (431.95)
a~CO-O~OH
Colensoic acid (Colensoinsaure)
HO~o~COOMe
CI Me
Needles (EtOAc), mp 234C

IH-NMR (CDCI3): 2.41, 2.43 (2x3H,2xs,2x-Me),
3.85 (3H,s,-COOMe), 10.51 (1H,s,-OH)
MS, m/z 436 (M+,3%), 434 (12), 432 (11), 402
(11),400 (13), 399 (14),397 (20), 367 (15), 365
(27), 339 (7), 337 (10), 187 (12), 186 (13), 149
(14), 105 (61),67 (100)
StL: Lecanora sulphurescens Fee
TLC: RF A: 0.58, B: 0.45, C: 0.48
Me
HPLC: Rj 28 5'"
Lit: Lumbsch and Elix 1993
Prismatic needles (MeOH-H 20), mp 173-174C
Chlorophyllopsorin (Chlorphyllopsorin) React: FeCl3 blue-violet
UV (MeOH): 256 (4.2), 310nm (3.3)
CIsH12CI207 (411.19) IR (KBr): 480, 495, 528, 542, 580, 594, 626, 638,
662, 690, 708, 750, 764, 785, 804, 835, 840, 862,
CI~CO-O~OMe 888, 940, 1010, 1048, 1115, 1140, 1160, 1190,

1202, 1214, 1240, 1274, 1292, 1328, 1350, 1418,
1460, 1564, 1580, 1605, 1635, 1742, 2860, 2920,
HO~O~CI 2950, 3080, 3450 cm- 1
CHO CHO MS, m/z 442 (M+), 424, 398, 226
Deriv: Methyl 2' -O-methylcolensoate, plates or
Cream crystals (CH 2CI2-cyclohexane), mp 228- prisms (MeOH), mp 87-88C, from colensoic
229C acid with CH2N2 in Et 20 at 20C in 24 h
React: PD yellow IH-NMR (60MHz,CDCI3 ): 0.70-1.15 (2x3H,
IH-NMR (CDCI3): 2.43, 2.59 (2x3H,2xs,2xMe-), m,Me-5",Me-5"'), 1.15-2.00 (12H,m,6x-CH 2 - ) ,
3.85 (3H,s,OMe), 9.90 (1H,s,-OH), 10.41, 10.46 2.60-3.20 (4H,m,-CH 2-1",-CH 2-1"'), 3.86 (3H,
(2xlH,2xs,2x-CHO) s,MeO-2'), 3.94 (3H,s,MeO-4), 3.99 (3H,s,-
MS, m/z 412 (M+,3%), 410 (5), 384 (3), 382 (5), COOMe), 6.67-6.88 (3H,m,H-3,H-5,H-3')
377 (33), 375 (100),349 (5), 347 (16), 213 (5),211 StL; Stereocaulon colensoi Bab.
(5), 200 (3), 198 (2) TLC: A: 41, B: 73, B': 66, C: 47
StL: Phyllopsora corallina (Eschw.) Mull.Arg. HPLC: Rj 41
var. ochroxantha (Nyl.) Brako MC: Fig. 37C
TLC: RF A: 0.72, B: 0.53, C: 0.73, E: 0.15 Lit: Fox et al. 1970; Djura and Sargent 1976b
3.17 Depsidones 317
a-Collatolic acid (a-Collatolsaure) 30.9, C-2"': 104.7, C-3"': 40.8, C-4"': 23.0, C-5"':
31.6, C-6 111 : 22.4, C-7 111 : 13.9, C-4-0Me: 55.7
C29H3409 (526.56)
MS, m/z 526 (M-), 508, 493, 491, 482, 466, 451,
440, 425, 413, 399, 383, 369, 355, 326, 297, 284,
7"
Me 280,269,262(1000/0),236,218,206,195,181,167,
150,138
Deriv: Methyl a-collatolate, leaflets (MeOH),

mp 122C, from a-collatolic acid with an
equimolar amount of CHzN z at C
StL: Tephromela atra (Huds.) Hafellner
TLC: A: 40, B: 32, B': 35, C: 35
HPLC: Rj 26
MC: Pig. 37B,D
Lit: c.P. Culberson 1969; Elix et al. 1974;
Krivoshchekova et al. 1983a; Huneck et al. 1996
Me Confumarprotocetraric acid
7'" (Confumarprotocetrarsaure)
Prisms (benzene-n-hexane), mp 124-125C; C22HlS012 (474.36)
hydrate (MeOH-H 20), mp 90-95C
React: KOH + NaOCI red, PeCl3 violet 9 8' ~COOH
UV (MeOH): 213 (4.58), 255 (4.08), 313nm
(3.56) 5~CO_O~~~CO
IR (KBr): 730, 780, 805, 862, 895, 1030, 1060,
1090, 1150, 1190, 1210, 1250, 1330, 1350, HO~O~COOH
1430, 1478, 1564, 1600, 1662, 1720, 2950, CH 2 0H Me
B 9'
3450cm-1
IH-NMR (500MHz,CDCI3, 20C): 0.90 (3H,t,J= Microcrystals (EtOAc-MeOH), mp 240-245C
7.1Hz,Me-7"'), 0.93 (3H,t,J=7.0Hz,Me-7"), 1.31 (dec.)
(4H,m,-CH 2-6",-CH2-6"'), 1.37 (4H,m,-CH z- IH-NMR (CD 30D): 2.44, 2.71 (2x3H,2xs,2x-,
5",-CH z-5"'), 1.59 (2H,m,-CH 2-4"'), 1.62 (2H, Me), 4.97 (2H,s,-CH z-8), 5.37 (2H,s,-CH z-8'),
m,-CH 2-4"), 2.00 (2H,m,-CH 2-3"'), 2.54 (2H,t, 6.57 (1H,s,H-5), 6.69, 6.71 (2x1H,2xs,-CH=CH-),
J=7.4Hz,-CH z-3"), 3.18, 3.52 (2x1H,2xd,J= 9.02, 11.87 (2x1H,2xs,2x-OH)
16.2Hz,-CH z-1"'), 3.84 (3H,s,MeO-4), 3.97 (2H, MS, m/z 209 (7%),151 (7), 149 (7), 135 (13), 128
m,-CH z-1"), 6.57 (1H,d,J=2.3Hz,H-5), 6.60 (1H, (11),127 (16),125 (51), 123 (13),99 (23),97 (14),
d,J=2.3Hz,H-3), 6.80 (1H,s,H-3'), 11.00 (1H, 55 (100)
s,HO-2') StL: Cladonia phyllophora Hoffm.
13C-NMR (125.6MHz,CDCI3): C-1: 113.8, C-2: TLC: A: 2, B: 2, C: 2; A: 7, B': 12, C: 6, G: 33
163.5, C-3: 104.6, C-4: 161.3, C-5: 115.2, C-6: Lit: EliX and Yu 1993; Elix and Ernst-Russell
141.2, C-7: 162.2, C-l': 104.9, C-2': 160.2, C-3': 1993
108.0, C-4': 150.5, C-5': 140.0, C-6': 129.3, C-7':
168.4, C-1": 47.9, C-2": 206.6, C-3": 42.7, C-4":
23.3, C-5": 31.3, C-6": 22.5, C-7": 13.9, C-1"':
Conhypoprotocetraric acid StL: Xanthoparmelia xanthosorediata Elix
:i
( Conhypoprotocetrarsaure) TLC: A: 50, B: 36, B': 31, C: 32, E: 18
HPLC: R] 20
ClsH160S (360.31)
Lit: Begg et al. 1979
oH
HO~O
Me CO-O OH Conorlobaridone (Conorlobaridon)
COOH
C21 H 22 0 6 (370.14)
Me Me
5"
Microcrystals, mp > 330 DC Me
IH-NMR (300MHz,CD 3 0D): 2.31, 2.36, 2.73
(3x3H,3xs,3x-Me), 4.76 (2H,s-CH z-OH, 6.55
(1H,s,H-5)
MS, m/z 165 (5%), 149 (17), 139 (10) 125 ( 18),
III (34),97 (56), 83 (60),71 (67),57 (100) HO
StL: Lecanora myriocarpoides Vain., Relicina
incongrua (Hale) Hale
TLC: A: 0.04, B: 0.12, C: 0.03, G: 0.21 Me
HPLC: R] 12 3'"
Lit: Elix et al. 1995d
Plates (acetone-cyclohexane), mp 179-180 DC
IH-NMR (acetone-d6): 0.81-1.79 (12H,m,2x-
Conloxodin Me,3x-CH z-), 2.77, 2.81 (2x 2H,2xt,J=8Hz,-
C23 H 24 0 S (428.14) CH z-2",-CH z-l"'), 6.64 (1H,s,H-3'), 6.87, 6.89
(2xlH,2xd,J=2.5Hz,H-3,H-5)
MS, m/z 370 (M+,IOO%), 342 (55), 313 (38),286
(32),233 (30),221 (8),220 (4)
StL: Xanthoparmelia xanthosorediata Elix
TLC: A: 43, B: 30, B': 33, C: 14, E: 20
HPLC: R] 17
Lit: Begg et al. 1979
Connorstictic acid (Connorstictinsaure)

ClsHl409 (374.29)
Crystals (CHC13 -CC14), mp 137 DC 9 8'

IH-NMR (CDC1 3 ): 1.20-1.80 (6H,m,Me-5",Me-
3"'), 2.72 (2H,t,J=8Hz,-CH z-2"), 3.18 (2H,t,J=
9Hz,-CH z-l"'), 3.96 (3H,s,-COOMe), 6.66-6.80
'5~co_~Me OH
(3H,m,H-3,H-5,H-3') HO~ 0
MS, m/z 428 (M+,100%), 396 (98), 384 (18), 370 CH 20H 0 HO 9' 0
(35), 221 (14), 220 (22) 8
3.17 Depsidones 319
Crystals (acetone), mp 280-300C (dec.) physodalic acid with MeJ-KzC0 3 in acetone

IR (KBr): 1250, 1292, 1445, 1610, 1710, 1745, StL: Flavoparmelia springtonensis (Elix) Hale
3400cm-1 TLC: A: 2, B': 11, C: 2, G: 24
IH-NMR (DMSO-d6 ): 2.20 (3H,s,Me-8'), 2.37 Lit: Elix et al. 1987b
(3H,s,Me-9), 4.78 (2H,s,-CH z-8), 6.73 (1H,s,H-
5), 7.05 (IH,s,H-9')
Conprotocetraric acid (Conprotocetrarsaure)
13C-NMR (DMSO-d6 ): 9.48, 20.66, 52,15, 98.77,
108.99, 111.10, 115.65, 117.21, 120.33, 135.79, ClsHl609 (376.31)
138.13, 143.45, 148.53, 151.52, 159.82, 161.52,
166.72 9 8'
MS, m/z 374 (M+), 356, 181, 179
~
Deriv: Tetraacetylconnorstictic acid, mp 238- Me eo_*eH20~H
240C (toluene-n-hexane), from connorstictic
acid with ACzO-H zS0 4 HO eOOH
o
StL: Pertusaria pseudocorallina (Lilj.) Arn. CH 20H Me
TLC: A: 11, B: 11, B': 11, C: 3, G: 26 8 9'
HPLC: R]3
Lit: O'Donovan et al. 1980; Elix and Lajide Microcrystals (EtOAc-MeOH), mp 230-235C
1981a; Elix and Ernst-Russell 1993 (dec.)
IH-NMR (CDPD): 2.35, 2.67 (2x3H,2xs,Me-9,
Me-9'), 4.68, 4.92 (2X2H,2xs,-CH z-8,-CH z-8'),
Conphysodalic acid (Conphysodalsaure)
6.55 (IH,s,H-5)
CZOHlSOIO (418.34) MS, m/z 149 (1 %),111 (1),97 (1), 85 (1),73 (100)
StL: Usnea trichodeoides Vain.
9 8'
TLC: RF A: 0.2, B: 0.2, C: 0.2; B': 7, C: 3, G: 9
~
Me co_:H2-:~COMe HPLC: Rl 12
Lit: Elix and Yu 1993; Elix and Ernst-Russell
1993
HO eOOH
o
eH 20H Me
8 9' Consalazinic acid (Consalazinsaure)
Microcrystals (acetone-n-pentane), mp > 230C ClsHl4010 (390.29)
(dec.)
IH-NMR (200MHz,acetone-d6 -DMSO-d6 ): 1.94 9 8'
(3H,s,-OAc), 2.40, 2.85 (2x3H,2xs,Me-9,Me-
9'),5.14,5.19 (2x2H,2xs,-CH z-8,-CH z-8'), 6.67
(lH,s,H-5).
5~eo_*-CH20::
13C-NMR (50.1 MHz,acetone-d6-DMSO-d6 ):
15.62, 20.73, 20.99, 55.07, 56.09, 111.48, 112.77,
HO~O
CH 20H HO 9' 0
113.70, 116.48, 116.91, 135.22, 143.34, 144.48, 8,
148.48, 159.77, 161.03, 162.03, 162.41, 170.67,
173.76 Crystals (acetone-HzO), mp 260C (dec.)
Deriv: Methyl di-O-methylconphysodalate, IR (KBr): 1130, 1260, 1475, 1610, 1692,
clustered needles, mp 155-156C from con- 1750cm-1
IH-NMR (DMSO-d6 ): 2.35 (3H,s,Me-9), 4.63, Consuccinprotocetraric acid

4.70 (2x2H,2xs,-CH z-8,-CH z-8'), 6.65 (1H,s,H- (Consuccinprotocetrarsaure)
5), 6.93 (IH,bs,H-9')
CZZHZOOIZ (476.38)

Deriv: Pentaacetylconsalazinic acid, needles
(EtOH-HzO), mp 164 DC, from consalazinic acid
9 8'
with ACzO-H zS0 4
StL: Parmotrema subisidiosum (Mtill.Arg.) Hale Me co_~CH20~~O~COOH
TLC: A: 2, B: 1, B': 1, G: 6
HPLC: Rr -l HO COOH
Lit: O'Donovan et al. 1980 o
CH 2 0H Me
8 9'
Constictic acid (Constictinsaure)
Microcrystals (EtOAc-MeOH), mp 237-240DC
C19H1401O (402.30) (dec.)

IH-NMR (CD 30D): 2.45, 2.78 (2x3H,2xs,Me-
9 S' 9,Me-9'), 2.52 (4H,s,-CH z-CH 2-), 4.94 (2H,s,-
Me co_*CH20~: CH 2-8), 5.27 (2H,s,-CH 2-8'), 6.63 (lH,s,H-5)
MS, m/z 121 (6%), 119 (19), 117 (18), 101 (14),
100 (9), 59 (100)
MeO 0 StL: Flavoparmelia succinoprotocetrarica Elix et
o
CHO HO 9' Johnston
8 TLC: A: 2, B: 2, C: 2, G: 15
Needles (acetone), mp 195-200DC HPLC: Rr 15
React: PD yellow-orange Lit: Elix and Yu 1993
UV (MeOH): 212, 310nm
IR (KBr): 790, 840, 890, 930, 968, 1020, 1090, Convirensic acid (Convirenssaure)
1142, 1160, 1220, 1265, 1298, 1388, 1440, 1463,
1548, 1600, 1682, 1732,2950, 3450cm-1
IH-HMR (60MHz,DMSO-d6 ): 2.48 (3H,s,Me-9),
4.67 (2H,s,-CH z-8'), 3.93 (3H,s,-OMe), 6.64
(1H,s,H-9'), 7.11 (1H,s,H-5), 10.49 (1H,s,CHO-
8)
MS, m/z 402 (M+)
Deriv: Pentaacetylconstictic acid, mp 210 DC,
from constictic acid with ACzO-H zS0 4
StL: Usnea aciculifera Vain.
TLC: A: 7, B: 3, B': 1, C: 2, G: 9, E: 0, F: 0 Needles (EtOAc-MeOH), mp 235-240 DC (dec.)
HPLC: Rr 1 IH-NMR (CDPD): 2.18, 2.38, 2.73 (3x3H,
MC: Fig. 38A 3xs,Me-9,Me-8',Me-9'), 4.95 (2H,s,-CH 2-8),
Lit: Yosioka et al. 1970 6.62 (lH,s,H-5)
MS, m/z 183 (1%), 168 (1),176 (1), 128 (13), 103
(22),94 (55), 93 (21),59 (100)
StL: Sulcaria virens (Taylor) Bystr. et D.
Hawksw.
3.17 Depsidones 321
TLC: A: 8, B': 26, C: 7, G: 37 Crystals (EtOAc-n-pentane), mp 245-246C

Lit: Elix and Yu 1993; Elix and Ernst-Russell React: PD yellow
1993 IH-NMR (CDCI 3): 2.27, 2.45, 2.59 (3x3H,
3xs,Me-9,Me-8',Me-9'), 3.98 (3H,s,-COOMe),
10.91 (IH,s,-CHO), 11.26, 12.92 (2x1H,2xs,2x-
Cryptostictic acid (Cryptostictinsaure)
OH)
C19H1609 (388.32) MS, mlz 406 (M+,17%), 374 (42), 346 (59), 318
(24), 290 (16), 276 (10), 213 (12), 140 (13), 106
9 8' (14), 91 (27), 77 (69),67 (100)
M.O-O~O:
StL: Cyclographa interposita Vain.
TLC: A: 68, B': 63, C: 70, E: 9
CHtJH O~
8
Lit: Naidu 1993; Elix and Ernst-Russell 1993
3-Dechlorodiploicin (3-Dechlordiploicin)
Needles (acetone-H 2 0), mp 242-244C (dec.) C16HllCl30S (389.62)

React: FeCl3 blue-purple 8
UV (EtOH) 214 (4.54), 267 (3.98), 316nm (3.51) Me Cl
IR (KBr): 1736,3110, 3370cm-1
lH-NMR (100MHz,DMSO-d6): 2.17 (3H,s,Me-
CI~CO-O~OMe
8'), 2.42 (3H,s,Me-9), 3.84 (3H,s,MeO-), 4.60
(1H,d,J=10Hz,-CH 2-8), 4.72 (1H,d,J=10Hz,-
HO~O~Cl
Me
CH 2-8), 6.92 (IH,s,H-9'), 6.92 (lH,s,H-5), 8.20 7'
(1H,s,-OH), 10.05 (IH,s,-OH)
MS, m/z 388 (M+), 370 (100%), 177 Crystals (MeOH), mp 272.5-274C
Deriv: Triacetylcryptostictic acid, mp 270- IR (CHCIJ: 1604, 1756cm-1
271.5C (dec.), from cryptostictic acid with lH-NMR (90MHz,CDCI3-DMSO-d6): 2.49, 2.52
Ac 2 0-H2 S04 (2x3H,2xs,Me-8,Me-7'), 3.85 (3H,s,-OMe),
StL: Lobaria oregana (Tuck.) MUll.Arg. 6.82 (IH,s,H-3)
TLC: A: 14, B: 14, B': 10, C: 10, G: 27 MS, mlz 392 (M+,10%), 390 (29), 388 (29), 357
HPLC: Rj 4 (14), 356 (14), 355 (70), 353 (100), 340 (13), 338
Lit: Shimada et al. 1980b (19), 327 (21), 326 (10),325 (29),311 (10),309
(16), 297 (10), 233 (11), 143 (10), 142 (11), 140
(10)
Cyclographin StL: Diploicia canescens (Dicks.) Massal.
C19H1SCIOs (406.76) TLC: A: 58, B': 53, C: 62, E: 28
HPLC: Rr 37
9 9' Lit: Sala et al. 1981
Me Me
CI*=o-XxCOOMe
HO OH
o
CHO Me
e 8'
3-Dechlorogangaleoidin MS, m/z 366 (M+,340/0), 365 (21), 364 (100), 334
(3-DechlorgangaIeoidin) (23), 332 (56), 306 (32), 304 (88), 292 (24), 291
(29), 290 (56), 276 (14), 264 (19), 248 (19), 237
CisHlSCI07 (378.75)
(25), 180 (32), 152 (22),69 (29), 67 (31)
Me StL: unnamed Lecidea sp.
CI~CO-O~31 OMe TLC: A: 56, B: 47, B': 40, C: 42, E: 17
HPLC: Rj 17
HO~
3 0
COOMe Lit: Chester et aI. 1979; McEwen and Sargent
1981
Me
Needles (CHzClz-n-pentane), mp 226-228C
IH-NMR (80MHz,CDCI3 ): 2.37, 2.54 (2x3H, 3-Dechloro-4-0-methyldiploicin
2xs,2x-Me), 3.78, 3.90 (2x3H,2xs,-OMe,- (3-Dechlor-4-0-methyldiploicin)
COOMe), 6.12 (1H,s,-OH), 6.66, 6.80 (2x1H, Cl7H 13 CI30 s (403.64)
2xs,H-3, H-3')
8
Deriv: 4-0-Methyl-3-dechlorogangaleoidin, Me Cl
needles (CHzClz-n-pentane), mp 240.5-241C,
from 3-dechlorogangaleoidin with MeJ and CI~CO-O~OMe
KZC0 3 in N,N-dimethylformamide
StL: Lecanora argentata (Ach.) Malme
MeO~o~CI
Me
TLC: Rp A: 0.53, B: 0.31, C: 0.40 7'
HPLC: Rj 23
Lit: Djura et al. 1976; Elix et al. 1994e Crystals (CHzClz-n-pentane), mp 230-231.5 c
IR (CCI4 ): 1598, 1758cm- 1
IH-NMR (60MHz,CDCI3 ): 2.47, 2.51 (2x3H,2xs,
3'-Dechlorolecideoidin (3' -Dechlorlecideoidin) Me-8,Me-7'), 3.81, 3.92 (2x3H,2xs,2x-OMe),
Cl7 H 13 CI0 7 (364.03) 6.59 (lH,s,H-3)
MS, m/z 406 (M+,140/0), 404 (28), 402 (28), 370
8 (21),369 (62),368 (24), 367 (100), 354 (17), 352
(28), 341 (26), 339 (35), 325 (17), 323 (19)
Clt(Me, 2' OH
t o - J4'93't 0 StL: Diploicia canescens (Dicks.) Massal.
5 2 5' l' 7' TLC: A: 74, B': 58, C: 83, E: 55
H0 4 3 0 6' COOMe Lit: Sala et al. 1981; Elix and Ernst-Russe111993
Me
8'
Dechloropannarin (Dechlorpannarin)
Crystals (toluene), mp 238C
IH-NMR (100MHz,CDCI3 ): 2.55, 2.68 (2x3H, ClsHl606 (328.31)
*=co-",
2xs,Me-8,Me-8'), 3.99 (3H,s,-COOMe), 6.78, 9 8'
6.86 (2X1H,2xs,H-3,H-3')
13C-NMR (67.8MHz,DMSO-d6): C-1: 113.0, C-2: 5 Me OM.
144.9, C-3: 105.1, C-4: 160.0, C-5: 119.4, C-6:
141.4, C-7: 161.7, C-8: 18.1, C-1': 119.1, C-2': HO 1
157.8, C-3': 105.5, C-4': 152.2, C-5': 140.8, C-6': o
CHO Me
128.5, C-7': 166.8, C-8': 12.8, 7'-COOMe: 52.1 8 7'
3.17 Depsidones 323
Needles (EtOAc-n-hexane), mp 182-184C Physical data unknown

React: PD yellow MS, mlz 399 (M-H+), 356, 328
IH-NMR (CDCI3 ): 2.21, 2.38, 2.52 (3x3H,3xs,3x- StL: Cladonia grayi Merr. ex Sandst.
Me), 3.79 (3H,s,-OMe), 6.46, 6.67 (2x1H,2xs,2x TLC: A: 41, B': 21, C: 18
arom.-H), 10.71 (1H,s,-CHO), 12.10 (lH,bs,-OH) HPLC: Rj 41
MS, mlz 328 (M+,100%), 314 (6), 300 (60), 285 LIt: C.F. Culberson et al. 1985; Elix and Ernst-
(87),284 (27), 241 (10),229 (10),214 (14), 199 Russell 1993
(ll), 192 (55), 179 (34), 178 (37), 177 (43), 151
(16), 150 (10), 134 (8), 122 (63), 107 (10)
4-0-Demethylnotatic acid
StL: Lecanora dispersa (Pers.) Sommerf.,
(4-0-Demethylnotatsaure)
Psoroma caesium Mull.Arg.
TLC: RF A: 0.76, B: 0.73, C: 0.78; A: 73, B: 73, B': C17H I4 0 7 (330.28)

61, C: 75, E: 55 9
Lit: Elix et al. 1982a; Leuckert et al. 1990a; Elix
and Ernst-Russell 1993 Me eo-;:yco ~,H
5-Dechlorovicanicin (5-Dechlorvicanicin)
HO
Me
o Me
eOOH
CI 8 H17CIO s (348.77) 8 8'
HO~:*:IM'
identified
MS, mlz 330 (M+), 312, 286, 284
StL: Ocellularia actinota (Tuck.) Mull.Arg.,
M' M' Parmelia columnata Hale
TLC: A: 16, B: 38, B': 35, C: 14, G: 46
HPLC: Rj 11
MS, m/z 350, 348 (M+)
Lit: C.F. Culberson and Hale 1973a
TLC: A: 52, B: 48, C: 40, E: 22
Lit: Elix and Ernst-Russell 1993 2'-0-Demethylpsoromic acid,
Conpsoromic acid, Neopsoromic acid
(2' -0-Demethylpsoromsaure,
4-0-Demethylgrayanic acid
Conpsoromsaure, N eopsoromsaure)
(4-0-Demethylgrayansaure)
C17H120S (344.27)
C22 H 2P7 (400.41)
4:
9 s'
Leo-o OH
Me
eo-"', OH
HO~ o eOOH
HO
, 0
1
CHO eOOH
8 7'
Crystals (acetone-H 20), mp 285C

React: PD yellow
Me
IR (KBr): 800,1117,1154,1268,1435,1575,1650, 8
Me
1690, 2500-3600 cm-1
IH-NMR (DMSO-d6): 2.20 (3H,s,Me-8'), 2.50 5JvCO-O~OH
HO~o/'jCOOMe
(3H,s,Me-9), 6.90 (1H,s,H-1'), 7.10 (1H,s,H-5),
10.53 (lH,s,-CHO)
Deriv: Methyl 2' -O-demethylpsoromate, mp Me
226C, from 2' -O-demethylpsoromic acid with 8'
CH2N2 at OC in 30 s Crystals (EtOAc-cyclohexane), mp 245C
StL: Usnea sp. from Venezuela. IH-NMR (CDC1 3 ): 2.34, 2.38 (2x3H,2xs,Me-8,
TLC: A: 15, B: 36, B': 39, C: 12, G: 46 Me-8'), 4.26 (2H,s,-COOMe), 6.96 (lH,s,H-3'),
HPLC: Rj 13 6.99, 7.03 (2X1H,2xd,J=2.3Hz,H-3,H-5), 9.82,
Lit: Keogh 1976 11.01 (2x1H,2xs,2x-OH)
MS, m/z 330 (M+,48%), 298 (36), 270 (58), 256
3-0-Demethylscensidin (47), 214 (21), 203 (32), 180 (28), 135 (48), 106
(32),77 (65), 69 (100),67 (97)
C16H12C120s (355.17) StL: Lecanora californica Brodo
8 TLC: RF A: 0.44, B: 0.29, C: 0.29
HPLC: Rj 0.22
~
Me 3'
Cl CO-O~OMe
Lit: Elix et al. 1994e
HO 3 O~CI 8',9'-Di-O-ethylsalazinic acid, Cetrariastrumin

Me (8',9' -Di-O-ethylsalazinsaure)
7'
CZ2H200U (444.38)
Needles (EtOAc-cyclohexane), mp 226-227.5C
IH-NMR (acetone-d6): 2.47 (6H,s,Me-8,Me-7'),
:(
9 8'
3.90 (3H,s,-OMe), 6.91, 6.93 (2x1H,2xs,H-3,H- Me CH20~Me
3'),9.85 (lH,bs,-OH) 6 , ~O-O 3' 2' OH
MS, mlz 358 (M+,5%), 356 (32),354 (49),328 (8), 2 4' "0
32l (31),319 (100), 187 (15),186 (1), 185 (6), 184 HO 4 3 0 5' 6' 7'
(4),172 (14), 170 (45) CHO 0 9' 0
StL: Diploicia canescens (Dicks.) Massal.
TLC: RF A: 0.60, B: 0.52, C: 0.53 8 Me)
HPLC: Rj 23
Lit: Elix et al. 1990b Needles (CHC1 3-MeOH), mp 163-165C
React: PD yellow
UV (MeOH): 212 (4.82),237 (4.76), 310nm (4.04)
Didechlorolecideoidin (Didechlorlecideoidin)
IR (KBr): 690, 810, 904, 966, 1028, 1040, 1100,
C17H I4 0 7 (330.23) 1142, 1162, 1208, 1258, 1296, 1342, 1360, 1392,
1456,1572,1654,1754,3040,3560cm-1
IH-NMR (200MHz,CDCI3 ): 1.23, 1.25 (2x3H,
2xt,J=7Hz,2x-CH 2-Me), 2.52 (3H,s,Me-9), 3.67
(2H,q,J=7Hz,-CH2-Me), 3.91, (2H,m,-CH 2-Me),
4.79 2H,q,J=12Hz,-CH 2-8'), 6.50 (1H,s,H-9'),
3.17 Depsidones 325
6.75 (1H,s,H-5), 8.50 (lH,bs,-OH), 10.47 (1H, Dinorscensidin

s,CHO-8), 12.14 (lH,s-OH)
CisHlOCl20S (341.14)
13C-NMR (50.29MHz,CDCl3): C-1: 109.3, C-2:
ME."
164.4, C-3: 111.9, C-4: 165.8, C-5: 118.3, C-6:
153.6, C-7: 167.8, C-8: 193.1, C-9: 22.2, C-1': Cl ~CO-O Yl(0H
100.3, C-2': 154.0, C-3': 120.7, C-4': 149.6, C-5':
138.7, C-6': 135.0, C-7': 159.7, C-8': 62.1, C-9': HO~O--rCI
110.6, 14.7, 15.2 (2X-O-CH z-Me), 65.9, 67.0 (2x- ME."
O-.G.H2-Me) Physical data unknown
MS, m/z 444 (M+,200/0), 398 (69), 369 (84), 354 StL: not yet found in lichens.
(24),341 (17),326 (30),314 (10), 299 (14),285 TLC: A: 46, B': 42, C: 32, E: 17
(20),256 (21), 185 (27), 179 (21), 177 (44), 167 Lit: Elix and Ernst-Russell 1993
(38), 150 (45), 149 (100), 137 (38), 129 (62), 125
(56),123 (51), 115 (38), 111 (83)
Deriv: 4,2'-Di-O-acetyl-8' ,9' -di-O-ethylsalazinic Diploicin
acid, mp 186-188 c (CHCl3 -MeOH), from 8',9'- Cl6HlOCl40S (424.07)
di-O-ethylsalazinic acid with ACzO-pyridine
StL: Cetrariastrum nepalensis Awas.
TLC: RF 0.81 (Si0 2, toluene: EtzO: AcOH=3: 6: 1)
Lit: Handong et al. 1984; Huneck and Tabacchi
1987
4,2'-Di-O-methylconnorstictic acid
(4,2' -Di-O-methylconnorstictinsaure)
Needles (EtOH or benzene), mp 232C
CZOH1S09 (402.34) UV (MeOH): 215 (4.30), 322nm (3.97)
9 8' IR (KBr): 685, 730, 745, 758, 780, 810, 820, 898,
965, 1010, 1030, 1050, 1075, 1120, 1190, 1220,
Meo4:o-:*.~e
1250, 1300, 1350, 1385, 1410, 1440, 1460, 1550,
1580, 1720,3000, 3450cm-1
lH-NMR (60MHz,DMSO-d6 ): 2.43, 2.58,
CH 20H 0 HO 9' 0 (2X3H,2xs,Me-8,Me-7'), 3.83 (3H,s,-OMe)
13C-NMR (25.05MHz,DMSO-d6 ): C-1: 113.2, C-
Mp not given 2: 155.3, C-3: 110.7, C-4: 153.9, C-5: 121.0, C-6:
lH-NMR (200MHz): 2.30' (3H,s,Me-8'), 2.53 128.3, C-7: 159.3, C-8: 18.1, C-l': 152.2, C-2':
(3H,s,Me-9), 3.75 (3H,s,C-4-0Me), 3.95 145.4, C-3': 117.1, C-4': 139.0, C-5': 150.0, C-6':
(3H,s,C-2' -OMe), 4.8 (2H,bs,-CH 2-OH), 6.69 139.0, C-7': 14.5,2'-OMe: 60.2
(1H,s,H-9'), 6.84 (1H,s,H-5) MS, m/z 428 (M+,50/0), 426 (15), 424 (30), 422
MS, m/z 402 (M+'140/0), 384 (13), 370 (100), 355 (20), 391 (35), 389 (92), 387 (100)
(24),326 (22), 257 (8),241 (10),207 (8), 191 (10), Deriv: 'O-Methyldiploicin, mp 220C, from
177 (50), 147 (15), 109 (15), 69 (58), 52 (55),43 diploicin with CH 2N 2
(45) StL: Diploicia canescens (Dicks.) Massal.
StL: Lobaria pulmonaria (1.) Hoffm. TLC: A: 65, B: 79, B': 65, C: 67, E: 13
Lit: Allemand 1988 HPLC: Rl 43
MC: Fig. 38B Prisms (acetone), mp 234-236C, silky needles

Lit: C.F. Culberson 1969; Hendrickson et al. (CHCI3-MeOH), mp 233-234C
1972; Djura et al. 1976; Sundholm and Huneck React: PD orange, FeCl3 red-brown
1981 UV (MeOH): 234 (4.18), S 254nm (4.06); MeOH
+ NaOH: 222 (4.15), 262 (4.15), 306 (3.98),
370 nm (3.56)
Divaronic acid (Divaronsaure)
IR (KBr): 722,738,800,828,874,906,954, 1010,
C21 H 22 0 7 (386.13) 1054, 1082, 1098, 1142, 1206, 1256, 1296, 1354,
1382, 1440, 1472, 1556, 1580, 1640, 1712, 2950,
3" 3500cm-1
Me IH-NMR (200MHz,CDCI3 ): 2.45, 2.56 (2x3H,
2" 2xs,Me-9, Me-7'), 3.86 (3H,s,-OMe), 10.68 (1H,
,11 I
CO-O 3 OH s,CHO-8), 12.80 (lH,s,-OH)

13C-NMR (50.3MHz,CDCI3 ): C-1: 114.0, C-2:
130.0, C-3: 119.9, C-4: 161.2, C-5: 110.8, C-6:
161.2, C-7: 163.0, C-8: 192.6, C-9: 19.9, C-1':
121.3, C-2': 150.7, C-3': 102.4, C-4': 142.6, C-5':
Me 142.8, C-6': 153.5, C-7': 14.4,2'-OMe: 56.6
3 f11 MS, m/z 386 (M+,130/0), 384 (75), 382 (100), 371
Crystals, mp 110 c, resolidification and melting (6), 369 (21), 367 (32), 349 (82), 347 (98), 319
again at 160-162C (60),260 (60), 233 (98), 198 (43), 170 (62)
IH-NMR (CDCI3 ): 0.95, 1.06 (2X3H,2xt,J= Deriv: Triacetyleriodermin, mp 221-223C,
7.5Hz,Me-3",Me-3"'), 1.43-1.80(4H,m,-CH z- from eriodermin with Ac 20-H 2S04
2",-CH2-2"'), 2.80, 3.23 (2X2H,2xt,J=7Hz,-CH z- StL: Erioderma physcioides Vain.
1",-CH z-1"'), 3.83 (3H,s,-OMe), 6.60, 6.68 TLC: A: 51, B': 64, C: 82, E: 57
(2x1H,2xd,J=2.2Hz,H-3,H-5), 6.70 (1H,s,H-3') HPLC: RJ 35
MS, m/z 386 (M+,1000/0), 368 (38),342 (28),340 Lit: Connolly et al. 1984b; Pulgarin et al. 1985a
(64),325 (16), 311 (18),297 (12), 285 (16), 245
(12), 193 (22), 192 (18), 177 (18), 164 (12), 149 Fulgidin
(24)
StL: Cladonia grayi Merr. ex Sandst. Cl6HllCl30S (389.62)
TLC: A: 35, B': 54, C: 42 8
Lit: C.F. Culberson et al. 1985; Elix et al. 1987f
CI~Meco_*C1,OM'
Eriodermin HO 1
o

CI Me
7'
9
Me 7 ' Prisms (CHCI3-n-hexane), mp 204-207C, crys-
CI 6 1 CO-)yA'3 2' OMe tals (MeOH), mp 207-209C
5 2 5' l' IR (CDCIJ: 1740cm- 1
HO 4 3 0 S' CI IH-NMR (300MHz,CDCI3-CD 30D): 2.50 (3H,s,
CHO Me Me-8), 2.56 (3H,d,J=0.47Hz,Me-7'), 3.88 (3H,s,
8 7' -OMe), 6.59 (lH,s,H-1')
3.17 Depsidones 327
MS, m/z 392 (M+,ll %), 390 (29), 388 (26), 357 Needles (acetone-H 20), mp 250-260C (dec.)
(13),356 (12), 355 (62),354 (25), 353 (100),329 React: KOH brown, PD orange-red
(6), 327 (13), 326 (7), 325 (20), 301 (5), 299 (8), UV (MeOH): 212 (4.50), 238 (4.29), 314nm
297 (14),223 (6),222 (3),221 (13),220 (7),219 (3.49)
(10), 218 (8), 155 (11), 139 (14), 127 (17), III IR (KBr): 708, 750, 765, 790, 810, 850, 880, 990,
(15) 1010, 1020, 1090, 1l25, 1150, 1200, 1230, l260,
StL: Fulgensia fulgida (Nyl.) Szat. 1290, 1360, 1380, 14l2, 1448, 1568, 1640, 1690,
TLC: A: 61, B': 49, C: 54, E: 11 1720, 2600, 3000, 3400 cm- l
Lit: Mahandru and Gilbert 1979b; Birkbeck et al. 13C-NMR (25.05MHz,DMSO-d6): C-I: 112.1, C-
1990; Elix and Ernst-Russell 1993 2: 165.6, C-3: 111.8, C-4: 164.6, C-5: 117.3, C-6:
152.3, C-7: 160.7, C-8: 191.7, C-9: 21.4, C-1':
115.4, C-2': 156.1, C-3': 113.2, C-4': 145.8, C-5':
Fulgoicin
142.1, C-6': 132.5, C-7': 170.7, C-8': 56.8, C-9':
C17H14C120s (369.19) 14.9, C-1": 164.1, C-2": 135.0, C-3": 132.5, C-4":
164.0
a 7' MS, m/z 358 (0.1%), 356 (0.2), 314 (1), 312 (1),
Me ME?
258 (1),230 (1), 152 (1), 151 (1), 116 (13),99 (19),
ClO-,OMe 98 (69), 88 (8),81 (8),72 (7), 71 (8),70 (5), 55 (9),
HO 1 54 (8), 53 (15),45 (36), 44 (100)
o Deriv: Heating of fumarprotocetraric acid in a
Cl ME? capillary to the melting point yields a sublimate
a' of crystalline fumaric acid, mp 287 DC
Crystals (MeOH), mp 224-226 DC StL: Cetraria islandica (1.) Ach.
IR (CHCI 3 ): 1740, 3510cm-1 TLC: A: 1, B: 25, B': 26, C: 7, G: 31
IH-NMR (100MHz,CDCI 3 ): 2.20, 2.51, 2.53 HPLC: R] 17
(3x3H,3xs,Me-8,Me-7',Me-8'), 3.79 (3H,s,- MC: Fig. 38C,D
OMe), 6.46 (1H,s,H-1') Lit: C.F. Culberson 1969; Sundholm and Huneck
MS, mlz 370 (M+), 368, 333, 325 1981
StL: Fulgensia fulgida (Nyl.) Szat.
TLC: C: 56
Furfuric acid (Furfursaure)
Lit: Mahandru and Gilbert 1979b; Mahandru
and Tajbakhsh 1983; Elix and Ernst-Russell 1993 C2sH24012 (552.47)
a"
Fumarprotocetraric acid Me
(Fumarprotocetrarsaure)
C22H16012 (472.35)
#:
4 '1
a'"
II
9 2
ME? CH 2- 0 1co ~COOH
6 1 ~O-O 3' 2' OH 3/1
2 4' r 7'
H0 4 3 0 5' 6' COOH 8
CHO ME'
8 9'
Crystals (CHCI 3), mp 250-254 DC (dec.) (25), 382 (22), 381 (37), 380 (26), 37l (7), 369
React: PD yellow (B), 367 (B), 365 (18), 356 (8), 355 (11), 354
IR (KBr): 1620,1685,3250, 3400cm-1 (18), 353 (14), 352 (15), 351 (10), 349 (10), 341
IH-NMR (200MHz,DMSO-d6 ): 1.96, 2.10, 2.23, (10), 339 (14), 338 (6), 337 (16), 327 (12), 326
2.43 (4x3H,4xs,4xMe-), 3.86 (3H,s,-COOMe), (11),325 (23),324 (14), 323 (7),311 (8),310 (5),
3.97 (2H,s,-CH 2-8), 6.76 (1H,s,H-5), 10.55 (1H, 309 (8),298 (5),297 (9), 296 (8),295 (8),294 (6),
s,CHO-8), 10.66, 11.87 (2x1H,2xs,2x-OH) 284 (5), 283 (5),282 (7), 281 (5),273 (6), 27l (8),
13C-NMR (50.29MHz,DMSO-d 6 ): C-1: 112.7, C- 221 (3), 219 (5), 218 (4), 194 (18), 191 (9), 190
2: 164.0, C-3: 111.7, C-4: 163.7, C-5: 116.9, C-6: (12), 177 (6), 176 (9), 174 (7), 173 (11), 166 (8),
151.6, C-7: 160.7, C-8: 191.7, C-9: 20.1, C-1': 151 (5)
118.5, C-2': 155.9, C-3': 113.7, C-4': 145.4, C-5': Deriv: Acetylgangaleoidin, prisms (CHCI3 -
142.5, C-6': 134.7, C-7': 171.0, C-8': 21.4, C-9': EtOH), mp 245-246 DC, from gangaleoidin with
14.4, C-1": 109.5, C-2": 157.2, C-3": 109.7, C-4": Ac 20-H 2S0 4
156.6, C-5": 119.7, C-6": 128.6, C-7": 171.1, C- StL: Lecanora gangaleoides Nyl.
8": 9.9, C-9": 17.8, 7"-COOMe: 51.7 TLC: A: 64, B: 43, B': 40, C: 54, E: 11
MS, m/z 552 (M+), 508, 375, 358, 223, 148, 127 HPLC: Rj 21
StL: Pseudevernia furfuracea (L.) Zopf. Furfuric MC: Figs. 63C,D; 64A
acid is probably an artefact Lit: Hendrickson et al. 1972; Sargent et al. 1975;
TLC: A: 12, B': 42, C: 28, G: 51 Djura et al. 1976; Cullen and Sargent 1981
Lit: Gunzinger and Tabacchi 1985a,b; Elix et al.
1987a
Glomelliferonic acid (Glomelliferonsaure)
C2sH 28 0 S (456.47)
Gangaleoidin
CIsH14CI207 (413.20) 5 11
*=
Me
8
M& 3'
Cl CO-::Y:oMe
HO COOMe
o
Cl Me
8'
Needles (acetone-EtOH), mp 214-215 DC

UV(MeOH): 208 (4.32); 320nm (3.68)
Me
IR (KBr): 700, 732, 776, 798, 808, 840, 868, 886, 5'"
954, 968, 1014, 1050, 1098, 1118, 1160, 1196,
1238, 1260, 1300, 1350, 1410, 1436, 1484, 1568, Plates (EtOAc-n-hexane), mp 184-185 D C
1596, 1680, 1720,2960, 3450cm-1 IR (Nujol): 1584, 1614, 1644, 1724, 1734cm- 1
IH-NMR (100MHz,CDCI3 -acetone-d6 ): 2.47 (6H, IH-NMR (CDCI 3 ): 0.95 (6H,t,Me-5",Me-5 111 ),
s,Me-8,Me-8'), 3.83, 3.89 (2x3H,2xs,-OMe,- 1.48-1.72 (8H,m,4x-CH 2 - ) , 2.52 (2H,t,]=7.1Hz,
COOMe), 6.74 (1H,s,H-3') -CH 2 -3"), 3.32 (2H,bs,-CH2 -1 111 ), 3.87 (3H,s,
MS, m/z 416 (M+, 13%),415 (14),414 (69),413 -OMe), 3.99 (2H,s,-CH 2-1"), 6.63, 6.72, 6.75
(22),412 (100), 386 (18), 385 (10), 384 (32), 383 (3x1H,3xs,H-3,H-5,H-3')
3.17 Depsidones 329
l~C-NMR (CDCU: C-1: 113.68, C-2: 162.57, C-3: TLC: A: 34, B': 24, C: 28
106.97, C-4: 160.86, C-5: 115.35, C-6: 139.08, C- HPLC: RJ 18
7: 163.02, C-1": 47.82, C-2": 205.96, C-3": 44.31, Lit: Elix et a1. 1987e
C-4": 16.94, C-5": 13.95, C-4-0Me: 55.46, C-1':
109.40, C-2': 162.38, C-3': 104.30, C-4': 148.41,
Grayanic acid (Grayansaure)
C-5': 141.24, C-6': 140.82, C-7': 172.77, C-1111:
27.76, C-2111: 30.87, C-3"': 32.20, C-4"': 22.28, C- C23H2607 (414.44)
5111 : 13.52
MS, m/z 456 (M+,3%), 439 (1),438 (2),412 (100), 8
235 (34),234 (39), 164 (6), 163 (3),71 (7) Me
StL: Neofuscelia subincerta (Ess1.) Ess1. 5~CO-O OH
TLC: A: 43, B': 40, C: 36
HPLC: Rr 26 Meo~o COOH
Lit: Elix et al. 1987e
Glomellonic acid (Glomellonsaure)

C2sHz609 (490.46)
5"
Me Crystals (EtOH-H 20), mp 186-189C (dec.)
React: KOH + NaOCI red ~ yellow, PeCl3
(EtOH) violet
UV (EtOH) 258 (4.10), 300-31Onm (3.5)
IR (CHCI3): 855, 1015, 1035, 1065, 1095, 1115,
1145, 1200, 1250, 1290, 1320, 1360, 1410, 1450,
1560, 1610, 1670, 1740,2850, 2950cm- 1
IH-NMR (90 MHz): 0.89 (3H,t,Me-7"), 1.26
(10H,bs,5x-CH z-), 2.50 (3H,s,Me-8), 3.24 (2H,
Me bs,-CH 2-1"), 3.83 (3H,s,-OMe), 6.62 (2H,s,H-
5'" 3,H-5), 6.72 (1H,s,H-3')
MS, m/z 414 (M+,100%), 396 (52), 370 (46), 368
Plates (EtOAc-n-hexane), mp 149-151C (30), 355 (10), 325 (34), 312 (80), 297 (30), 283
IR (Nujol): 1572, 1612, 1674, 1724, 1754cm-1 (28),270 (12), 269 (14),257 (30),244 (28), 229
IH-NMR (CDCI 3): 0.94 ,(6H,t,J=6.6Hz,Me- (20),217 (30),191 (22), 165 (98)
5",Me-5"'), 1.63 (2H,sextet,J=6.6Hz,-CH 2-4"'), Deriv: Acetylgrayanic acid, mp 57-59C (ben-
2.09, 2.53 (2X2H,2Xt,-CH 2-3",-CH 2-3 111 ), 3.52 zene-n-hexane), from grayanic acid with Ac 20-
(2H,s,-CH 2-1"), 3.83 (3H,s,-OMe), 3.97 (2H,s,- H 2 S0 4
CH 2-1 111 ), 6.59 (2H,d,J=2.2Hz,H-3,H-5), 6.78 StL: Cladonia grayi Merr. ex Sandst.
(lH,s,H-3') TLC: A:. 38, B: 62, B': 59, C: 44
MS, m/z 453 (27%),452 (100), 382 (28),235 (14), HPLC: RJ 37
234 (20),164 (4),163 (3),71 (4); chemical ioniza- MC: Pig. 39A
tion: m/z 471 (M+H, 1.4%),470 (4.3) Lit: C.P. Culberson 1969; Djura and Sargent
StL: Neofuscelia subincerta (Ess1.) Ess1. 1976a; c.P. Culberson et al. 1985
3-Hydroxycolensoic acid 3-Hydroxyphysodic acid

(3-Hydroxycolensoinsaure) (3-Hydroxyphysodsaure)
CZSH300S (458.49) CZ6H3009 (486.50)
5" 7"
Me Me
4"
3'
OH
OH
MeO
OH eOOH
Me
5"1
Me
5'"
Prisms (CHCI3 -cyclohexane), mp 163-165C
UV (MeOH): 218, 302nm Needles (MeOH-HzO), mp 187C; plates (ac-
lH-NMR (100MHz,CDCI3 ): 0.62-1.06 (6H,m, etone-benzene), mp 193-194C
Me-5",Me-5"'), 1.13-1.93 (12H,m,6x-CH z-), React: FeCl3 bluish violet
2.80 (2H,t,benzyl.-CH z-), 3.41-3.57 (2H,m, IR (KBr): 1605, 1620, 1660, 1690, 3150,
benzyl.-CH z-), 3.96 (3H,s,-OMe), 6.64, 6.73 3550cm-1
(2X1H,2xs,H-5,H-3'), 8.64 (2H,bs,2x-OH) lH-NMR (90MHz,DMSO-d6 ): 0.88 (3H,t,J=6Hz,
MS, m/z 458 (M+,990/0), 441 (13), 440 (36), 416 -Me), 0.92 (3H,t,J=6Hz,-Me), 1.11-2.11 (12H,
(8),415 (32),414 (100),413 (16),412 (12),401 bs,6x-CHz-), 2.42 (2H,t,J=7Hz,-CH z-3"), 3.04
(5),399 (7), 398 (8), 397 (15), 388 (20),387 (79), (2H,bs,-CH z-1"'), 3.82 (2H,s,-CH z-l"), 6.52,
386 (10), 385 (10),384 (2), 383 (13),373 (6),372 6.56 (2XIH,2xs,H-5,H-3')
(15),370 (12), 369 (17), 358 (9), 357 (20), 356 (7), MS, m/z 443 (4%),442 (14),265 (17),264 (98),
355 (15),345 (6),344 (19), 343 (73),341 (9),330 263 (14),248 (16), 208 (16),207 (34), 192 (6)~ 181
(5),329 (13), 327 (12),316 (9), 315 (12),313 (5), (5),180 (37), 179 (22),166 (17),165 (5), 163 (6),
301 (9),287 (5), 259 (5), 245 (5),238 (7),237 (47), 151 (5), 150 (10),129 (5), 138 (16), 137 (24), 133
236 (79), 233 (9), 221 (5), 218 (6), 208 (6), 207 (5),125 (12), 124 (100),123 (32),95 (7),91 (6),81
(19),205 (5), 193 (12), 190 (7) (9), 79 (6), 77 (14), 69 (24), 67 (12), 66 (7), 65
Deriv: Methyl di-O-methylhydroxycolensoate, (11), 63 (7), 57 (5), 55 (20), 53 (14), 52 (6), 51
prisms (MeOH), mp 115-116.5C, from 3- (12),44 (88),43 (14),41 (21)
hydroxycolensoic acid in EtOAc with CHzN z at Deriv: Triacetyl-3-hydroxyphysodic acid, mp
20C in 1 h 104C, from 3-hydroxyphysodic acid with
StL: Hypotrachnya formosana (Zahlbr.) Hale Acz'o- HzSO 4
TLC: A: 39, B: 50, B': 50, C: 42 StL: Hypogymnia enteromorpha (Ach.) Nyl.,
HPLC: RT 7.35 min Hypogymnia physodes (L.) Nyl.
MC: Fig. 64B,C,D TLC: Rp 0.36 (n-hexane:Et 20:HCOOH = 13:8:
Lit: Djura et al. 1977a,b 2); A: 15, B: 36, B': 34, C: 13
3.17 Depsidones 331
HPLC: RJ 17
Lit: Hirayama et al. 1974, 1976a; Elix 1975; Cl*Me co_~Me OH
Hebrard et al. 1975; Jones et al. 1976; Elix and
Engkanian 1976a; Elix and Ernst-Russell 1993 HO eOOMe
a
Me Me
Hypoconstictic acid (Hypoconstictinsaure) Crystals (CHCI 3 ), mp 238-240C
Cl9Hl609 (388.32) IH-NMR (CDCIJ: 2.25, 2.43, 2.49, 2.66 (4x3H,
4xs,4x-Me), 3.96 (3H,s,-COOMe), 6.18, 11.50
9 a' (2x1H,2xs,2x-OH)
MeO~O:O~~:
MS, m/z 392 (M+,28%), 362 (5), 360 (16), 334
(12),332 (33),307 (5), 306 (6), 305 (16),304 (11),
294 (6), 292 (19),280 (9),278 (32),265 (7), 199
~
(7), 194 (20), 83 (100)
Me StL: Erioderma phaeorhizum Vain.
B TLC: Rp A: 0.63, B: 0.58, C: 0.52, E: 0.34
Lit: Hamat et al. 1993
Microcrystals (acetone-toluene), mp 260-264 c
IH-NMR (200MHz,CDCl3-DMSO-d6): 2.28, 2.44
(2x3H,2xs,Me-8,Me-9), 3.87 (3H,s,-OMe), 4.74 Hypoprotocetraric acid
(2H,s,-CH 2-8'), 5.48 (bs,-OH), 6.62 (1H,s,H- (H ypoprotocetrarsa ure)

9'),6.73 (1H,s,H-5), 8.25, 10.10 (2x1H,2xbs,2x- ClsHl607 (344.31)
OH) 9 a'
13C-NMR (50.1 MHz,CDCl 3-DMSO-d6): 8.32,
20.69, 53.43, 55.63, 96.0, 109.08, 110.28, 112.53, Me, ~o_Me21 OH
114.48, 122.07, 136.99, 137.84, 141.67, 148.27, 4 2 I 7'
152.32,158.69, 160.91, 161.08, 166.14 HO 0 6' eaOH
MS, m/z 354 (1 %),336 (0.5), 317 (1),310 (1), 309 Me Me
(2), 253 (7), 161 (22), 149 (53), 146 (81), 105 8 9'
(100)
Needles (acetone), mp 242-243C (dec.)
Deriv: Triacetylhypoconstictic acid, mp 190-
React: FeCl3 (EtOH) blue
192C, from hypoconstictic acid with Ac 20-
UV (EtOH): 216 (4.59), 262 nm (4.09)
pyridine
IR (Nujol): 701, 716, 737, 757, 787, 854, 1020,
StL: Nephroma antarcticum (Wulf.) Nyl.,
1073, 1138, 1190, 1263, 1395, 1415, 1495, 1580,
Xanthoparmelia metastrigo~a (Elix) Hale
1620, 1650, 1685, 3490cm-1
TLC: A: 15, B: 7, B': 7, C: 4, G: 28
IH-NMR (270MHz,DMSO-d6): 2.11 (3H,s,Me-
HPLC: Rl 7
8'), 2.21 (3H,s,Me-8), 2.29 (3H,s,Me-9), 2.50
Lit: Moroney et al. 1981; Elix et al. 1985a
(3H,s,Me-9'), 6.62 (lH,s,H-5)
MS, m/z 344 (M+,21 %), 326 (ll), 300 (32), 298
Hypophysciosporin (20), 28'S (8),271 (7),258 (12),244 (17), 216 (13),
136 (ll), 108 (8), 91 (14),57 (28),44 (100)
Cl9Hl7CI07 (392.78)
Deriv: Diacetylhypoprotocetraric acid, mp
190.5-191.5C (MeOH), from hypoprotoce-
traric acid with Ac20-H 2S0 4
13C-NMR (25.05MHz,CDCI3): C-l: 119.4, C-2: IR (KBr): 840, 1129, 1264, 1582, 1612, 1700cm-1
160.2, C-3: 120.0', C-4: 152.8, C-5: 122.1, C-6: IH-NMR (DMSO-d6): 2.20, 2.27, 2.33 (3x3H,
141.5, C-7: 161.8, C-8: 10.3, C-9: 20.5, C-l': 3xs,3xMe-), 6.63 (IH,s,H-5), 6.66 (IH,s,H-9')
122.9, C-2': 145.2b, C-3': 122.5', C-4': 147.4, C- MS, mlz 358 (M+,760/0), 340 (100), 314 (72), 313
5': 144.7b, C-6': 128.0, C-7': 170.0, C-8': 10.7, C- (36), 312 (51), 286 (26), 285 (28), 284 (34), 258
9': 14.9, .GH3-CO-: 20.2-20.8, CH3-.GO-: (16),257 (29), 256 (29), 230 (I8), 229 (31), 228
167.8-170.1; values marked with a and b may be (22), 165 (68)
exchanged Deriv: Triacetylhyposalazinic acid, mp 203-
StL: Ramalina hypoprotocetrarica W.Culb., 205C, from hyposalazinic acid with Ac2 0-pyri-
Ramalina tumidula (Tayl.) Hun. et Follm. dine
TLC: A: 25, B: 43, B': 37, C: 22, G: 48 StL: Xanthoparmelia quintaria (Hale) Hale
HPLC: R, 19 TLC: A: 34, B: 27, B': 26, C: 8, G: 44
MC: Fig. 39B,C,D HPLC: R, 8
Lit: C.F. Culberson 1969; Sundholm and Huneck Lit: Asahina and Shibata 1954; Keogh 1978;
1981; Sala and Sargent 1981 Moroney et al. 1981
Hypopsoromic acid (Hypopsoromsaure) Hypostictic acid (Hypostictinsaure)

ClsHl607 (344.31) Cl9Hl60S (372.32)
Ho~Oo-*OM'
*
9 8'
Me CO_~M.0:
ME' COOH MeO 4
o 0
Needles (EtOH-H 20), mp 230C Me HO 9'
8
TLC:A: 25, B: 32,C: 17
Needles (acetone), mp 263-264 c (dec.)
Lit: Asahina and Shibata 1954; Elix and Ernst-
IR (KBr): 1560, 1605, 1695, 1750cm-1
Russell 1993
IH-NMR (pyridine-ds): 2.43 (3H,s,Me-9), 2.62
(3H,s,Me-8'), 2.67 (3H,s,Me-8), 3.83 (3H,s,-
Hyposalazinic acid (Hyposalazinsaure) OMe), 6.82 (IH,s,H-5), 7.52 (1H,s,H-9')
MS, m/z 372 (M+,650/0), 354 (100), 328 (88),327
ClsHl40S (358.29)
(60), 326 (77), 300 (24), 299 (28), 298 (40), 272
(18), 271 (29), 244 (I8), 243 (22), 242 (28), 216
HO~:-O~O:
(40), 179 (21)
Deriv: Diacetylhypostictic acid, mp 244C, from
~
hypostictic acid with AczO-pyridine
StL; Xanthoparmelia quintaria (Hale) Hale
Me
TLC: A: 50, B: 33, B': 32, C: 32, G: 61
Needles (acetone-H 2 0), mp 280C (dec.) HPLC: R, 13
React: KOH yellow -7 red-brown, FeCl3 purple, Lit: Asahina and Shibata 1954; Keogh 1978;
H 2S0 4 deep red Moroney et al. 1981
3.17 Depsidones 333
Isidiophorin MS, mlz 392, 390 (M+), 388, 357

StL: Hafellia dissa (Stirt.) Mayrh.
C22HlS09 (426.36)
TLC: A: 66, B': 58, C: 52, E: 28
HPLC: Rr 6.69 min
Lit: Birkbeck et al. 1990; Elix and Ernst-Russell
1993
MeO Isonotatic acid (Isonotatsaure)

Cl8Hl607 (344.31)
Crystals, mp 268-270C 5 Leo_Me OH

UV (EtOH): 267 (4.46), 301 nm (4.27)
IR (KBr): 960, 1150, 1330, 1550, 1590, 1600,
Meo~
3 0
eOOH
1670 cm-l Me
IH-NMR (DMSO-d6): 2.21 (3H,s,Me-8'), 2.44
Rosettes (acetone-n-hexane), mp 166-16rc
(3H,s,Me-12), 2.52 (3H,s,Me-9), 3.97 (3H,s,
(dec.)
MeO-4), 6.49 (IH,bs,H-9'), 7.04 (IH,s,H-5),
IH-NMR (CDCI3-acetone-d6 ): 2.38, 2.51, 2.80
7.05,7.95 (2xIH,AB-d, J=17Hz, H-8,H-I0), 8.08
(3x3H,3xs,3x-Me), 3.89 (3H,s,-OMe), 6.78 (2H,
(IH,s,HO-9'), 10.16 (lH,s,HO-2')
s,H-3,H-5), 10.21 (2H,bs,-OH,-COOH)
13C-NMR (DMSO-d6): C-l: 112.8, C-2: 166.3, C-
MS, m/z 344 (M+'1000/0), 326 (55), 300 (22), 298
3: 113.4, C-4: 161.8, C-5: 112.2, C-6: 148.2, C-7:
(86), 285 (9), 272 (23), 258 (32), 244 (I8), 243
159.9, C-8: 132.7a, C-9: 21.0, C-I0: 131.7a, C-11:
(23), 165 (32), 149 (23), 135 (9), 120 (I4)
199.1, C-12: 26.9, C-l': 109.1, C-2': 151.9, C-3':
Deriv: Methyl isonotate, rosettes, mp 172-173 c
120.6, C-4': 146.3, C-5': 137.8, C-6': 135.6, C-7':
(EtOAc-n-hexane), from isonotatic acid with
160.0, C-8': 9.5, C-9': 95.6. Values marked by a
CH 2N2 at OC in 30s
may be exchanged
StL: Ramalina americana Hale, Xanthoparmelia
MS, mlz 426 (M+), 408, 382, 191, 189, 188,43
notata (Kurok.) Hale
StL: Lobaria isidiophora Yoshim.
TLC: A: 38, B': 42, C: 43, G: 56
Lit: Bo et al. 1990
HPLC: Rj 24
Lit: Elix and Lajide 1984a; c.P. Culberson et al.
Isofulgidin 1990a
Cl6HllCI30s (389.62)
Isovicanicin
C\ *CO-Oyy0Mo
HO~o~a el~eO-O*OH
CI Me
Needles (CH 2CI2-n-hexane), mp 260-261C, Meo~o---yei
softening at 200-210C M& M&
Needles (EtOAc-n-hexane), mp 247-249C Leoidin

IH-NMR (acetone-d6 ): 2.24, 2.44, 2.48, 2.51
co-xx
(4x3H,4xs,4x-Me), 3.85 (3H,s,-OMe)
MS, m/z 384 (M+,48%), 382 (70), 349 (35), 348
(33),347 (100),294 (12), 292 (60), 215 (5),218
(8),170 (12),160 (12), 146 (12),125 (12),90 (12), CI*Me Me OH
83 (14), 77 (15)
HO CaOMe
StL: Psoroma atrophyllum Stirt. o
TLC: A: 68, B: 77, B': 68, C: 70, E: 55 Cl Me
HPLC: Rr 35
Lit: Elix et al. 1982a; Elix and Ernst-Russel11993 Crystals (benzene), mp 232-233 DC
IR (KBr): 1580, 1665, 1730, 3370cm-1
IH-NMR (pyridine-ds): 2.36, 2.57, 2.75 (3x3H,
Lecideoidin 3xs,3x-Me), 3.80 (3H,s,-COOMe)
C17H I2 CI2 0 7 (397.99) MS, m/z 414 (M+), 412
StL: Lecanora gangaleoides Nyl.
B TLC: A: 62, B': 54, C: 52
Me Cl
HPLC: R[ 36
C I t (to-o
' 3' i OH Lit: Elix and Ernst-Russell 1993
5 2 4' " 7'
HO 4 3 0 5' 6' COOMe
Me
Lividic acid (Lividsaure)
B'
C27 H 32 0 9 (500.53)
Crystals (toluene), mp 247 DC
IH-NMR (100MHz,CDCI 3): 2.55, 2.65 (2x3H, 7"
Me
2xs,Me-8,Me-8'), 3.98 (3H,s,-COOMe), 6.80
(1H,s,H-3)
13C-NMR (67.8MHz,DMSO-d6 ): C-1: 112.3, C-2:
142.5, C-3: 105.2, C-4: 159.8, C-5: 119.7, C-6:
141.7, C-7: 160.5, C-8: 18.1, C-1': 119.7, C-2':
158.1, C-3': 110.8, C-4': 148.9, C-5': 141.9, C-6':
126.8, C-7': 166.4, C-8': 12.8, 7-COOMe: 52.5
MS, m/z 398 (M+,78%), 368 (40), 367 (20), 366
(77),365 (40),364 (60), 363 (100),338 (30),333
(40), 332 (46), 331 (90), ,305 (27), 304 (52), 303
(53), 291 (47), 290 (29), 264 (22), 169 (22), 77
Me
(22),67 (48) 5'"
Deriv: Di-O-methyllecideoidin, mp 184-185 DC
(cyclohexane-toluene), from lecideoidin with Needles, mp 209-210 DC (dec.)
CH 2N2 in EtOAc in 20 min React: KOH yellowish, KOH + NaOCI red-
StL: unnamed Lecidea sp. brown, FeCl3 (EtOH) blue-violet
TLC: A: 48, B: 47, B': 35, C: 40, E: 4 IR (KBr): 740, 800, 860, 922, 1024, 1075, 1116,
HPLC: R[ 24 1138, 1192, 1228, 1265, 1278, 1310, 1416,
Lit: Chester et al. 1979; McEwen and Sargent 1460, 1510, 1602, 1646, 1706, 2880, 2950,
1981 3450cm-1
3.17 Depsidones 335
IH-NMR (60MHz,acetone-d6 ): 0.55-0.98 (6H,m, IR (KBr): 735, 780, 830, 850, 990, 1030, 1050,
Me-7",Me-5"'), 1.00-1.70 (12H,m,6x-CH 2- ) , 1120, 1150, ll90, 1208, 1270, 1362, 1410, 1470,
2.40 (2H,t,J=7Hz,-CH 2-3"), 3.51 (2H,bt,J=7Hz,- 1565, 1600, 1660, 1685, 17l0, 3000, 3250 cm- 1
CH 2-1"'), 3.82 (3H,s,-OMe), 3.91 (2H,s,-CH z- IH-NMR (400MHz,DMSO-d 6 ): 0.95 (6H,t,Me-
1"),6.61,6.75 (2xlH,2xs,H-5,H-3'), 11.00 (3H, 5",Me-5"'), 1.41 (2H,m,-CH l -4"), 1.45 (2H,m,-
bs,2x-OH,-COOH) CH z-4"'), 1.54 (2H,m,-CH 2-3"'), 1.73 (4H,
MS, m/z 456, 279, 278, 262 -CH 2-3",-CH z-3"'), 2.84 (2H,t,-CH z-2"), 3.10
Deriv: Methyllividata, mp 185-186C (EtOAc- (2H,t,-CH z-l"'), 3.90 (3H,s,4-0Me), 6.74 (lH,
n-hexane), from lividic acid with CH 1N 2 at 20C d,H-3), 6.75 (1H,d,H-5), 6.77 (1H,s,H-3'), 11.03
in 2 min (1 H,s,H 0-2')
13C-NMR (CDCl3): C-1: ll4.1, C-2: 146.6, C-3: 13C-NMR (25.05MHz,DMSO-d6 ): C-1: llLl, C-
134.1, C-4: 149.0, C-5: llO.5, C-6: 129.0, C-7: 2: 162.7, C-3: 105.9, C-4: 164.1, C-5: 111.5, C-6:
161.2, C-1": 47.1, C-2": 205.0, C-3": 42.1, C-4": 140.7, C-7: 162.0, C-1": 202.9, C-2": 41.1, C-3":
23.1, C-5": 31.0, C-6": 22.2, C-7": 13.8, C-4- 25.5, C-4": 22.0, C-5": 13.9, C-4-0Me: 56.5, C-
OMe: 55.8, C-1': 108.4, C-2': 158.8, C-3': 106.4, 1': 120.1, C-2': 152.9, C-3': 105.9, C-4': 148.6, C-
C-4': 147.6, C-5': 141.0, C-6': 138.1, C-7': 169.5, 5': 144.5, C-6': 134.1, C-7': 168.3, C-l"': 31.4,
C-l"': 32.0, C-2"': 31.0, C-3"': 27.5, C-4"': 22.2, C-2"': 30.5, C-3"': 27.4, C-4"': 21.6, C-5"': 13.9
C-5"': 14.0, 7-COOMe: 51.9 MS, m/z 456 (M+,220/0), 412 (98), 398 (12), 384
StL: Hypotrachyna livida (Tayl.) Hale (14), 355 (18), 327 (13), 312 (11), 300 (9), 235
TLC: A: 32, B: 35, B': 37, C: 31 (21), 205 (17), 192 (20), 188 (32), 149 (14), 123
HPLC: R] 20 (44),97 (14), 69 (13), 55 (19),44 (100)
Lit: C.P. Culberson 1969; Elix and Engkanian Deriv: Methyl lobarate, needles (MeOH), mp

1976a; Jones et al. 1976 122C, from lobaric acid with an equimolar
amount of CH 2N2 at C
StL: Protoparmelia badia (Hoffm.) Hafellner
Lobaric acid (Lobarsaure) TLC: A: 30, B: 46, B': 47, C: 38
CZ5HzsOs (456.47) HPLC: R] 30
MC: Pig. 40A
5" Lit: c.P. Culberson 1969; Sundholm and Huneck
Me 1981
Loxodellonic acid (Loxodellonsaure)

C23H240S (428.42)
5"
Me
Me
5'"
Prisms (acetone), mp 196-197C

React: KOH faint yellow, PeCl3 violet
UV (MeOH): 212 (4.54), 260 (3.96), 295 nm
(3.78)
Plates (EtOAc-n-hexane), mp 159-161 c Deriv: Methyl di-O-methyllobarate, needles

IR (Nujol): 1584, 1609, 1659, 1724, 1744cm-1 (MeOH), mp 102C, from loxodin with an ex-
IH-NMR (CDCI3 ): 0.94, 1.10 (2x3H,2xt,J=6.5Hz, cess of CH2N 2 at 20C in 3 days
Me-5",Me-3 111 ), 1.54-1.70 (4H,m,-CH 2 -4",- StL: Xanthoparmelia fLavescentireagens (Gyeln.)
CH2-2111 ), 2.53 (2H,t,J=6.5Hz,-CH 2-3"), 3.30 Hale, Xanthoparmelia furcata (Mull.Arg.) Hale
(2H,bs,-CH 2-1 111 ), 3.86 (3H,s,-OMe), 3.96 TLC: A: 50, B: 40, B': 40, C: 36, E: 28
(2H,s,-CH2-1"), 6.60, 6.70 (2xlH,2xd,J=2.5Hz, HPLC: RJ 28
H-3,H-5), 6.72 (1H,s,H-3') MC: Fig. 40B
!3C-NMR (CDCI3 ): C-l: 113.97, C-2: 162.71, Lit: Komiya and Kurokawa 1970
C-3: 108.03, C-4: 161.71, C-5: 115.82, C-6:
139.55, C-7: 163.49, C-l": 48.26, C-2": 207.46,
Malonprotocetraric acid
C-3": 44.91, C-4": 17.34, C-5": 14.30, C-l':
(Malonprotocetrarsaure)
107.94, C-2': 162.54, C-3': 104.69, C-4': 149.96,
C-5': 141.89, C-6': 141.02, C-7': 173.67, C- C21H16012 (460.34)
1111: 29.83, C-2111: 24.81, C-3"': 13.86, C-4-0Me:
55.82
MS, m/z 384 (100%), 235 (39),234 (52), 164 (9),
163 (1), 71 (5)
StL: Neofuscelia subincerta (Essl.) Essl.
TLC: A: 38, B': 35, C: 35
Lit: Elix et al. 1987e; Elix and Ernst-Russell 1993
Loxodin, methyl norlobarate Crystals (acetone), mp 280C (dec.)

(N orlobarsauremethylester) React: PD orange-red
IR (KBr): 1208, 1260, 1275, 1650, 1690, 1735,
C2sH2S0S (456.47)
1752 cm-l
IH-NMR (60MHz,DMSO-d6 ): 2.50 (3H,s,Me-9),
Me
2.51 (3H,s,Me-9'), 3.37 (2H,s,-CH 2-2"), 5.25
(2H,s,-CH 2-8'), 6.81 (IH,s,H-5), 10.60 (1H,s,-
CHO-8)
OH MS, m/z 356, 314, 312
StL: Parmotrema conformatum (Vain.) Hale
HO COOMe TLC: A: 2, B': 16, C: 4, G: 27
HPLC: RJ 17
Lit: Keogh 1977
Me
Menegazziaic acid (Menegazziasaure)
Crystals (CHC!J, mp 132-133.5C ClsHl409 (374.29)
UV (EtOH): 289 (3.98), 320nm (3.93)
IR (KBr): 1437,1578,1608,1672, 1713cm-1
MS, m/z 456 (M+,100%), 428 (32),424 (54), 398
(22), 396 (18), 367 (19), 341 (53), 221 (27)
3.17 Depsidones 337

8 8' UV (MeOH): 216 (4.60), 258 (4.08), 300nm
Me co_~M. 0: (3.78)
IR (KBr): 748, 810, 868, 912, 1024, 1080, ll20,
ll40, 1200, 1244, 1270, 1350, 1410, 1462, 1503,
MeO 1560, 1600, 1648, 1730,2860,2950, 3450cm-1
o 0
IH-NMR (60MHz,CDCI3): 0.70-1.10 (6H,bt,Me-
OH HO 9'
5", Me-5"'), 1.10-2.00 (12H,m,6x-CH z-), 2.65-
Crystals (dioxane-H20), mp 272-273C 3.10 (2H,t,J=7Hz,benzyl.-CHz-)' 3.30-3.75 (2H,
React: FeCl3 (EtOH) violet bt,J=7Hz,benzyl.-CHz-), 3.96, 4.01 (2x3H,2xs,
IR (KBr): 1619, 1727, 1766, 3400cm-1 2x-OMe), 6.68, 6.73 (2X1H,2xs,H-5,H-3'),
IH-NMR (90MHz,DMSO-d 6 ): 2.17, 2.34 (2x3H, 13.35 (2H,bs,-OH,-COOH)
2xs,Me-8,Me-8'), 3.84 (3H,s,-OMe), 6.78 (lH, MS, m/z 472 (M+,190/0), 454 (5), 442 (5), 429 (64),
s,H-5), 6.78 (lH,s,H-9') 428 (100),413 (17),398 (37), 396 (36),387 (30),
MS, mlz 300 (480/0), 285 (14),272 (2),244 (3),181 386 (65), 385 (35), 384 (50), 373 (16), 372 (44),
(13),180 (13), 179 (10), 151 (50) 371 (40), 358 (27), 357 (21), 356 (68), 344 (24),
Deriv: Triacetylmenegazziaic acid, needles (di- 343 (45), 342 (16), 341 (35), 330 (45), 329 (48),
0xane-H2o)' mp 222C, from menegazziaic acid 327 (ll), 316 (28),315 (41),301 (22),287 (16),
with ACzO-H 2S0 4 273 (27), 251 (53), 250 (77), 224 (24), 207 (38),
StL: Menegazzia asahinae (Yas. ex Zahlbr.) 194 (14), 179 (24), 168 (29), 167 (34), 166 (52),
Sant., Menegazzia terebrata (Hoffm.) Mass. 151 (18),137 (16), 124 (24)
TLC: A: 19, B': 14, C: 12, G: 36 Deriv: Methyl 0-methyl-3-methoxycolensoate,
HPLC: RJ 5 prisms (MeOH), mp 105-10rC, from 3-
Lit: Hirayama et al. 1976c methoxycolensoic acid with an excess of CH zN 2
in Et 20 at 20C in 3 days
3-Methoxycolensoic acid StL: Hypotrachyna livida (Tayl.) Hale
(3-Methoxycolensoinsaure) TLC: A: 44, B': 61, C: 47
HPLC: RT 13.86min
Cz6H 32 0 S (472.52) MC: Fig. 67A,B
Lit: Djura et al. 1977a,b
5"
Me
4-0-Methyl-5-dechlorovicanicin
(4-0-Methyl-5-dechlorvicanicin)
CI9HI9CIOs (362.79)
MeO
5~CO-O~OMe
Me
MeO~O~CI
5'" Me Me
Prisms (MeOH-HzO), mp 120-122C Physical data unknown

React: KOH + NaOCI red-brown, FeCl3 (EtOH) MS, m/z 464, 362 (M+)
violet StL: not yet found in lichens
TLC: A: 75, B: 64,C: 76,E:61 IH-NMR (CDCI3 ): 2.37, 2.59 (2x3H,2xs,

Lit: Elix and Ernst-Russell 1993 Me-9,Me-8'), 3.81 (3H,s,-OMe), 3.98 (3H,s,-
COOMe), 10.16 (1H,s,CHO-8), 12.82 (1H,s,-
OH)
Methyl 5,1' -dichloronorpsoromate
MS, m/z 444 (M+,<l %),442 (5),440 (7),414 (5),
(5,1' -Dichlornorpsoromsauremethylester)
413 (2), 412 (9), 411 (3), 408 (8), 407 (37), 406
ClsH12Cl20S (427.19) (24),405 (100), 379 (2), 377 (5),213 (2), 211 (3)
StL: Phyllopsora corallina (Eschw.) Mull.Arg.
9 8' var. ochroxantha (Nyl.) Brako
TLC: Rp A: 0.73, B: 0.60, C: 0.78, E: 0.27
CIMe
co_*MeOH HPLC: RT 6.69 min
5 " Lit: Elix et al. 1990f
HO o Cl
CHO COOMe
8 7' 4-0-Methyldiploicin
Cream microcrystals (CH 2CI2-n-hexane), mp C17H12CI4 0 s (438.10)

230-232C, softening at 215C
M':::~'
React: PD yellow
IH-NMR (CDCI3 ): 2.35, 2.58 (2x3H,2xs,Me-
9,Me-8'), 3.98 (3H,s,-COOMe), 10.16 (lH,s,-
CHO-8), 12.82 (2H,s,2x-OH)
MS, m/z 430 (M+,4%) 428 (23), 426 (35), 393 CI Me
(22),391 (70),363 (9),362 (6),361 (28),360 (16), Crystals (benzene), mp 220C
359 (78),216 (5), 215 (5),214 (ll), 213 (15), 211 MS, m/z 440 (M+,6%), 438 (29), 436 (22), 405
(15),186 (5), 185 (8), 184 (10), 183 (6) (38),404 (20),403 (99),402 (22),401 (100),388
StL: Phyllopsora corallina (Eschw.) Mull.Arg. (10),386 (10), 375 (24),373 (25),359 (9),357 (9),
var. ochroxantha (Nyl.) Brako 345 (6),237 (3.5), 235 (5),233 (4)
TLC: Rp A: 0.55, B: 0.47, C: 0.50, E: 0.17 StL: Diploicia canescens (Dicks.) Massal. ssp.
HPLC: RT 5.41 min australasica Elix et Lumbsch
Lit: Elix et al. 1990f TLC: A: 84, B: 85, C: 90, E: 68
HPLC: RT 14.41 min
Methyl 5,1'-dichloropsoromate Lit: Spillane et al. 1936
(5,1' -Dichlorpsoromsauremethylester)
C19H14Cl20S (441.21) 4-0-Methylhypophysciosporin
C2oH19CI07 (406.80)
H:~~*~IM'CHO COOMe
Microcrystals (EtOH-H 20), mp 204.5-207C

React: PD yellow
3.17 Depsidones 339
Needles (acetone), mp 200-203C 3-0-Methyllividic acid (3-0-Methyllividsaure)

IH-NMR (CDCI3): 2.24, 2.44, 2.48, 2.66 (4x3H,
4xs,4x-Me), 3.83 (3H,s,C-4-0Me), 3.96 (3H,s,- C27H3407 (470.54)
COOMe), 11.53 (1H,s,-OH) 7"
MS, m/z 408 (M+, 11 %), 406 (36), 376 (6), 374 Me
(15),348 (13),346 (39), 321 (5),319 (15), 308 (6),
306 (19),294 (10), 292 (31),213 (5), 194 (36),173
(24), 83 (100)
StL: Erioderma phaeorhizum Vain.
TLC: Rp A: 0.72, B: 0.67, C: 0.76, E: 0.49
Lit: Hamat et al. 1993
4-0-Methylhypoprotocetraric acid
(4-0-Methylhypoprotocetrarsaure)
Cl9Hl807 (358.33) Me
5U1
5~CO-O~OH Needles (CH 2Cl2-n-pentane), mp 156.5-159C

IH-NMR (CDCI 3 ): 0.88-0.94 (6H,m,Me-7",Me-
MeO~o~COOH Sill), 1.24-1.65 (12H,m,6x-CH 2-), 2.57 (2H,t,-
CH 2-3"), 3.40 (2H,bt,-CH 2-1 111 ) , 3.92 (2H,s,
Me Me
-CH 2-1"), 3.91, 3.96 (2x3H,2xs,2x-OMe), 6.58,
Needles (dimethylformamide), mp 228-229C 6.76, (2x1H,2xs,H-5,H-3'), 11.2-11.4 (2H,bs,-
(dec.) OH,-COOH)
UV (EtOH): 217 (4.57),264 (4.14), 312nm (3.54) MS, mlz 470 (M+,100%), 293 (16),292 (42),277
IR (Nujol): 1650, 1740, 3400 cm-l (38),263 (16),221 (12),207 (14)
IH-NMR (60MHz,DMSO-d6-dimethylforma- StL: Hypotrachyna livida (Tayl.) Hale
mide): 2.21, 2.32, 2.48, 2.61 (4x3H,4xs,4x-Me), TLC: Rp A: 0.41, B: 0.46, C: 0.39
3.94 (3H,s,-OMe), 6.94 (1H,s,H-5) HPLC: RJ 68.6
MS, m/z 358 (M+,9%), 340 (4), 315 (21), 314 Lit: Elix and Venables 1993
(100), 312 (10), 300 (8), 299 (21), 259 (8), 258
(41),257 (21), 245 (9),244 (5), 243 (25),231 (7),
230 (10),215 (7), 179 (14), 178 (5), 157 (6), 136 4-0-Methylpannarin
(13),128 (8),123 (6), 107 (5), 106 (5),91 (21),83 C19 H 17 Cl0 6 (376.78)
(16),79 (7), 78 (5),77 (12),67, (9), 65 (13),63 (5),
M.:#Oo-*OM.
55 (7), 53 (7), 51 (8),44 (98),43 (7),41 (9) ME' Me
Deriv: Methyl 4-0-methylhypoprotocetrarate,
prisms (benzene), mp 219-220C, from 4-0-
methylhypoprotocetraric acid with CH 2N 2 at
20C in 2 min
CHO Me
StL: Xanthoparmelia notata (Kurok.) Hale
TLC: A: 35, B: 58, B': 51, C: 45, G: 61 Physical data unknown
HPLC: RJ 28 React: PD orange
Lit: Cresp et al. 1972, 1975; Sala and Sargent 1981 MS, m/z 378, 376 (M+), 227, 225
StL: not yet found in lichens 2' -O-Methylphysodic acid

TLC: A: 70, B: 56, C: 71, E: 53 (2'-0-Methylphysodsaure)
Lit: Elix and Ernst-Russell 1993
CZ7H3Z0S (484.53)
4-0-Methylphysodic acid 7"

(4-0-Methylphysodsaure) Me
CZ7H3Z0S (484.53)
7"
Me
3'
OMe
HO COOH
3 0
3'
OH
COOH Me
3 5 111
Crystals (acetone-benzene-cyclohexane), mp
160-162C
Me
5'" IR: 1620,1700, 1730,2860,2960, 3300cm- I
IH-NMR (100MHz,CDCI3-acetone-d6 ): 0.88 (6H,
Plates (benzene-acetone-n-pentane), mp 151- bt,Me-7",Me-5111 ), 1.18-1.74 (12H,m,6x-CH z-),
152C 2.51 (2H,bt,-CH 2-3"), 2.80 (2H,m,-CH z-l l11 ) ,
React: KOH + NaOCI red, FeCl3 (EtOH) blue- 3.72 (3H,s,-OMe), 3.89 (2H,s,-CH 2-1"), 6.46
violet (1H,s,H-3'), 6.58 (2H,s,H-3, H-5), 7.82 (2H,bs,-
UV (EtOH): 211 (4.67), 260nm (4.15) OH,-COOH)
IR (Nujol): 1575, 1620, 1650, 1735, 1740cm-I MS, miz 441 (10%),440 (32),397 (6), 385 (8),384
IH-NMR (60MHz,acetone-d6 ): 0.90 (6H,t,Me- (34),383 (17),370 (9), 369 (15), 355 (8),285 (11),
7",Me-5 111 ), 1.50 (12H,m,6x-CH 2 - ) , 2.52 (2H,t,- 271 (7),257 (5),249 (17),248 (15),193 (10), 192
CH z-3"), 3.28 (2H,t,-CH 2 -1 111 ), 3.86 (3H,s, (31), 177 (10),176 (5), 163 (15), 153 (9), 151' (5),
-OMe), 4.06 (2H,s,-CH z-1"), 6.66-6.84 (3H,m, 150 (12),149 (6), 138 (12), 137 (27),136 (5),135
3xarom.-H), 11.00 (3H,s,-OH) (5), 134 (8), 125 (5), 124 (7), 121 (7), 105 (6),99
MS, m/z 484 (M+), 440, ,263, 262 (6),91 (11),77 (5),71 (7), 69 (5),55 (6),45 (15),
Deriv: Methyl 4-0-methylphysodate, plates 44 (100),43 (18),41 (9)
(Et2 0-n-hexane), mp 124.5-125C, from 4-0- Deriv: Benzyl 2'-0-methylphysodate, mp 107-
methylphysodic acid with an equimolar amount 108C, from 2'-0-methylphysodic acid with
of CH 2N 2 at OC ethereal phenyldiazomethane
StL: Hypotrachyna livida (Tayl.) Hale StL: Hypogymnia billardieri (Mont.) R. Filson
TLC: A: 39, B: 43, B': 45, C: 42 TLC: A: 39, B: 34, B': 28, C: 22
MC: Fig. 40C,D HPLC: RI21
Lit: C.F. Culberson 1969; Elix 1975 Lit: Elix 1975
3.17 Depsidones 341
Methylstictic acid (Methylstictinsaure) Methyl virensate (Virenssauremethylester)

C2oHl609 (400.33) Cl9Hl60S (372.32)
9 8'
5~CO-O~OH
M.O~O-O~O:
CHO O~
8
HO~o~COOMe
CHO
8
Me
Needles (acetone or EtOAc), mp 215-216.5 DC

Needles (acetone), mp 250-251 DC (dec.)
React: KOH weak yellow, PD yellow, FeCl3
React: PD orange, FeCl3 purple
(EtOH) red
UV (EtOH): 238 (4.62), 312nm (3.77)
UV (MeOH): 242, 310nm
IR (KBr): 1695, 1740, 1755, 3370cm-1
IH-NMR (CDCI3 ): 2.28, 2.53, 2.58 (3x3H, 3xs,
IH-NMR (I00MHz,DMSO-d6): 2.22 (3H,s,Me-
8'), 2.48 (3H,s,Me-9), 4.44 (3H,s,C-9' -OMe), 3x-Me), 3.96 (3H,s,-OMe) 6.70 (IH,s,H-5),
10.71 (IH,s,-CHO)
3.91 (3H,s,C-4-0Me), 6.44 (IH,s,H-9'), 7.08
MS, m/z 372 (M+, 63%), 340 (34),313,312 (81),
(IH,s,H-5), 10.30 (IH,s,-OH), 10.39 (IH,s,-
285 (47),284, 272 (77), 258 (100),245 (18),230
CHO)
(16),217, 194, 179, 177, 152, 151
MS, m/z 400 (M+,100%), 368, 340, 193, 191
StL: Lobaria oregana (Tuck.) Milll.Arg. Deriv: Methyl di-O-methylvirensate, needles
(benzene-n-hexane), mp 160-162 DC, from me-
TLC: A: 50, B': 15, C: 38, G: 49
thyl virensate with dimethyl sulphate and K2CO 3
Lit: Shimada et aL 1980b
m acetone
StL: Pseudocyphellaria Javeolata (DeL)
4-0-Methylvicanicin MaIme
TLC: A: 72, B': 55, C: 77, E: 50
Cl9HlsCl20S (397.24)
Lit: Renner et aI. 1978; Pulgarin and Tabacchi
1989
Cl~CO-O~OM.
Norargopsin
MeO~o~Cl C17H12C1206 (383.18)
Me Me
H:~::i:1H
Needles (benzene), mp 193-'194 DC
MS, m/z 398 (M+), 396, 363, 361
StL: Erioderma sp. from Malaysia
TLC: A: 84,B: 85,C:90,E:68
HPLC: RT 14.41 min CHO Me
Lit: Neelakantan et aL 1962; Elix et aL 1982a; 8'
1990b
Needles (CH 2Clz-cyclohexane), mp 152-154 DC
React: PD yellow-orange
H04:0-*0"
IH-NMR (200MHz,CDCI3 ): 2.31, 2.44, 2.59 (3x
3H,3xs,3x-Me), 5.72 (lH,s,-OH), 10.70 (lH,s,-
CHO), 12.78 (lH,s,-OH)
MS, m/z 382 (M+,73%), 386 (9), 384 (48), 347
(100),215 (7),213 (21) CHO Me
StL: Erioderma chilense Mont.
TLC: A: 62, B': 63, E: 29
MS, m/z 314 (M+), 286, 179, 177
StL: Lecanora dispersa (Pers.) Sommerf.
TLC: A: 51, B': 46, C: 40, E: 28
Norcolensoic acid (Norcolensoinsaure) Lit: Leuckert et al. 1990a
CZ4Hzs07 (428.46)
N organgaleoidin
5"
Me C17H 12 Clz0 7 (399.18)
*=
8
Me 3'
OH Cl CO-~OH
HO eOOMe
HO eOOH o
e[ Me
8'
Crystals (MeOH), mp 242-243C
Me IR (KBr): 1663, 1750, 3400 cm-l
5'" IH-NMR (100MHz,acetone-d6 ): 2.44, 2.64 (2x
3H,2xs,2x-Me), 3.92 (3H,s,-COOMe), 6.75 (1H,
Crystals (EtOAc-cyclohexane), mp 235-240C s,H-3')
(dec.) MS, m/z 402 (M+), 400, 398 (70%),366 (60), 338
IH-NMR (CDCI3 ): 0.72-0.96 (6H,m,Me-5", Me- (97), 219 (15),218 (18)
5111 ), 1.16-1.60 (12H,m, 6x-CH z-), 2.44-2.76 StL: Lecanora chlarotera Nyl.
(4H,m,-CH z-1",-CH z-1 111 ), 6.60 (3H,bs,H-3, H- TLC: A: 59, B': 40
5,H-3'), 9.20 (3H,2x-OH,-COOH) HPLC: Rr 15
MS, m/z 384 (100%), 356 (14),343 (15),341 (11), Lit: Mahandru and Gilbert 1979a; Elix and
329 (10), 328 (11), 316 (17), 299 (19), 286 (15), Ernst-Russel 1993
271 (15),206 (22),44 (62)
StL: Lecanora sp. from 'Australia
TLC: A: 28, B: 54, B': 53, C: 31 Norisonotatic acid (Norisonotatsaure)
Lit: Chester and Elix 1981b
Nordechloropannarin (N ordechlorpannarin)
Cl7Hl406 (314.28)
LCO-O~OH
HO~o~eOOH
Me
3.17 Depsidones 343
Physical data unknown Needles (acetone-H 2 0), mp 207-209C

StL: Ramalina americana Hale IR (KBr): 730, 750, 850, 862, 1006, 1024, 1050,
Lit: c.P. Culberson et al. 1990a 1072, 1122, 1154, 1196, 1220, 1270, 1312, 1350,
1408,1456, 1480, 1600, 1700,3000, 3430cm-1
IH-NMR (60MHz,CDCI3 ): 2.32 (6H,s,2x-Me),
Norlobaridone (Norlobaridon)
2.72 (3H,s,-Me), 6.58 (2H,s,H-5,H-3')
C23H2606 (398.44) MS, mlz 330 (M+,lOOO/O), 312 (25), 288 (8), 287
(15), 286 (75), 284 (31), 279 (5), 270 (11), 244
Me (19),242 (8),230 (11),229 (5),216 (6), 165 (16),
164 (6), 149 (19)
StL: Xanthoparmelia weberi (Hale.) Hale
Lit: Djura and Sargent 1977
OH
HO Norpannarin
C17H 13 Cl0 6 (348.72)
Me Me
H:~::x!oH
Me
Needles (EtOH-H 2 0 or benzene), mp 188C

React: FeCl3 (CHCI3-pyridine) blue, but no CHO Me
colour with FeCl3 in EtOH
UV (EtOH): 270 nm (3.96) Yellowish prisms (EtOAc-cyclohexane), mp
IR (Nujol): 1680, 3250 cm-1 198-202C
Deriv: Diacetylnorlobaridone, needles (EtOH- IH-NMR (200MHz,CDCU: 2.24, 2.32, 2.59
H 20), mp 104C from norlobaridone with (3x3H,3xs,3x-Me), 6.45 (lH,s,H-1'), 10.68 OH,
Ac20-H 2S0 4 s,-CHO), 12.78 (2H,bs,2x-OH)
StL: Xanthoparmelia conspersa (Ehrh.) Hale, MS, m/z 348 (M+,1000/0), 350 (34),215 (7),213
Xanthoparmelia scabrosa (Tayl.) Hale (18)
TLC: A: 40, B: 36, B': 36, C: 20, E: 18 StL: Erioderma chilense Mont.
HPLC: R] 26 TLC: A: 51, B': 48, C: 42, E: 21
MC: Fig. 41A,B Lit: Elix et al. 1986
Norstictic acid (Norstictinsaure)
Nornotatic acid (Nornotatsaure) C1s H 12 0 9 (372.28)
C17 H I4 0 7 (330.28)
Me
*
CO~_31 OH
HO eOOH
o
Me Me
Needles (acetone), mp 286-287C (dec.) IR (Nujol): 1739, 3450cm-1

React: KOH yellow -7 red, precipitate of deep lH-NMR (100MHz,CDC13-DMSO-d6): 2.28, 2.42,
red needles, PD orange, FeC13 wine red 2.48,2.50 (4x3H,4xs,4x-Me)
UV (MeOH): 212 (4.48),239 (4.40), S 270 (4.02), MS, m/z 372 (M+,14%), 371 (15), 370 (65), 369
3.17nm (3.70) (20), 368 (100), 355 (11), 353 (18), 335 (36), 334
IR (KBr): 790, 805, 860, 904,930,968,1018,1065, (31),333 (100),332 (37),314 (11), 312 (15), 305
1095, 1142, 1160, 1200, 1248, 1290, 1370, 1442, (25), 279 (30), 278 (16), 277 (86), 201 (12), 200
1490,1562, 1642, 1700, 1744,3000, 3430cm-1 (7), 199 (36), 198 (12), 185 (12), 184 (15), 172
lH-NMR (60MHz,DMSO-d6): 2.22, 2.46 (2x3H, (14),170 (40), 154 (12),119 (13), 91 (14),83 (11),
2xs,Me-9,Me-8'), 6.86 (IH,s,H-5), 6.90 (1H,s, 77 (12)
H-9'), 10.48 (1H,s,-CHO) StL: Psoroma sphinctrinum (Mont.) Nyl.
J3C-NMR (25.05MHz,DMSO-d6): C-l: 111.6, C- (chemical strain II)
2: 166.1, C-3: 110.4, C-4: 164.0, C-5: 117.2, C-6: TLC: A: 68, B: 55, B': 58, C: 63, E: 36
152.2, C-7: 160.0, C-8: 192.6, C-9: 21.3, C-l': Lit: Sargent et al. 1976
109.0, C-2': 151.9, C-3': 120.7, C-4': 147.7, C-5':
137.3, C-6': 135.5, C-7': 163.4, C-8': 9.3, C-9':
Notatie acid (Notatsaure)
95.4
MS, m/z 372 (M+,100%), 354 (70), 343 (8), 327 ClsHl607 (344. 31)
(50), 298 (28), 281 (9), 269 (18), 244 (21), 221
(11),216 (25), 179 (51), 177 (49), 150 (20), 106 Me
(21) 5NCO-O~OH
Deriv: Pentaacetylnorstictic acid, prisms
(CHC13-MeOH), mp 212C, from norstictic acid MeO~o~COOH
with Ac2 0-H 2 S04 Me Me
StL: Pleurosticta acetabulum (Neck.) Elix et
Lumbsch Needles (acetone), mp 225-226C (dec.)
TLC: A: 40, B: 29, B': 32, C: 30, G: 57 UV (EtOH): 218 (4.56), 264 (4.09), S 312nm
HPLC: Rl 12 (3.49)
MC: Figs. 41C,D; 42A,B IR (Nujol): 1665, 1700, 3100-3200cm-1
Lit: C.F. Culberson 1969; Sundholm and Huneck lH-NMR (60MHz,DMSO-d 6 ): 2.29 (3H,s,Me-),
1981; Gohrt, unpubl. results 2.46 (6H,s,2x-Me), 3.91 (3H,s,-OMe), 6.72, 6.91
(2xIH,2xs,H-5, H-3')
MS, m/z 344 (M+,99%), 345 (20), 326 (21), 301
Norvieanicin
(19), 300 (100),299 (12), 298 (31), 286 (8), 285
(17),284 (26), 273 (11),272 (6),271 (6),260 (42),
259 (11),258 (49),257 (10),256 (12),245 (8),244
:~~o:*:~
(29), 243 (38), 242 (8), 234 (10), 233 (66), 232
(17),231 (19),230 (22), 229 (14), 217 (14),216
(6),215 (18), 180 (7), 179 (62), 178 (28), 165 (5),
163 (17), 152 (11), 151 (8), 150 (25), 149 (17),148
Me Me (5),147 (6),136 (7), 135 (6), 134 (8), 128 (6), 123
Needles (cyclohexane-toluene), mp 248-249C (5),122 (14), 121 (7), 119 (5), 116 (9), 115 (8), 107
UV (EtOH): 230 (4.27),270 (3.97), S 323 (2.90), S (8), 103 (7),92 (5),91 (34),89 (5), 83 (10),82 (7),
330 nm (2.84) 79 (9), 78 (17),77 (20), 69 (20),67 (19), 66 (5),65
3.17 Depsidones 345
(27),64 (6), 63 (ll), 55 (11),53 (12),52 (10), 51 HPLC: RJ 37

(18), 50 (7),44 (100), 43 (22),41 (15) MC: Fig. 42C
Deriv: Methyl notatate, rosettes (benzene), mp Lit: C.F. Culberson 1969; Huneck and Lamb
203-204 DC, from notatic acid with CH1Nz at 1975; Jackman et al. 1975
20 DC in 2 min
StL: Xanthoparmelia notata (Kurok.) Hale
Phyllopsorin
TLC: A: 24, B: 49, B': 44, C: 38, G: 55
HPLC: RJ 19 C1sH 13 CI0 7 (376.73)
Lit: Cresp et al. 1972, 1975; Djura and Sargent
1977 9 7'
Pannarin
H:~:*,OMe
CHO ,CHO
9 7' 8 8
CI*Meco_Me, OM, Microcrystals (EtOAc), mp 233.5 DC

IH-NMR {CDCIJ: 2.33, 2.60 (2x3H, 2xs,2x-Me),
HO 1 3.88 (3H,s,-OMe), 7.06 (1H,s,H-l'), 10.20 (IH,
CHO a
8
Me
8'
s,-OH), 10.26, 10.68 (2xlH,2xs,2x-CHO)
MS, m/z 378 (M+,80/0), 376 (24), 350 (11), 348
(35), 213 (16), 211 (17) 187 (19), 185 (50), 166
Needles (acetone), mp 216-217 DC (49), 164 (31)
React: PD orange, FeCl3 (EtOH) red StL: Phyllopsora corallina (Eschw.) Miill.Arg.
UV (MeOH): 212 (4.22), 234 (4.15), S 250nm var. ochroxantha (Nyl.) Brako
(4.04) TLC: RF A: 0.66, B': 0.45, C: 0.64, E: 0.08
IR (KBr): 700, 710, 728, 768, 790, 838, 890, 910, HPLC: RT 4.85 min
980, 1000, 1024, 1080, 1134, 1164, 1204, 1224, Lit: lix et al. 1990f
1250, 1300, 1350, 1386, 1420, 1440, 1466, 1500,
1550, 1584, 1600, 1640, 1720,2950,3500 cm-1
IH-NMR (270 MHz,CDCI 3): 2.22 (3H,s,Me-7'), Physciosporin, Methyl 5-chlorovirensate
2.38 (3H,s,Me-8'), 2.59 (3H,s,Me-9), 3.81 (3H,s, (5-Chlorvirenssauremethylester)
MeO-2'), 6.46 (1H,s,H-l'), 10.70 (1H,s,CHO-8), C19HlSCIOs (406.76)
12.80 (1H,s,HO-4)
MS, m/z 362 (M+,840/0), 349, (4), 347 (16), 345
(14), 336 (12), 335 (19), 334 (35), 333 (43), 319 CI*Meco_::Me OH
HO
(31), 305 (12), 303 (14),213 (14), 211 (10), 178
(51),122 (100), 83 (14),77 (33), 67 (21), 51 (17),
CHO o
COOMe
43 (10) Me
Deriv: Triacetylpannarin, prisms (EtOH), mp
208 DC, from pannarin with ACzO-HzS04 Needles (acetone-EtzO), mp 201-202 DC
StL: Lecanora subaurea Zahlbr., Pannaria React: PD orange
conoplea (Ach.) Bory UV (EtOH): 216 (4.54), 250 (4.46), 318nm (3.74)
TLC: A: 73, B: 68, B': 63, C: 79, E: 40, F: 64 IR (KBr): 1641, 1660, 1733,2845,2926, 2964cm-1
IH-NMR (100MHz,CDCI3): 2.28, 2.58, 2.60 142.2, C-6': 131.9, C-7': 170.3, C-8': 55.5, C-9':
(3x3H,3xs,3x-Me), 3.97 (3H,s,-COOMe), 10.73 14.5
(1H,s,-CHO), 11.41, 12.81 (2xIH,2xs,2x-OH) MS, m/z 356, 314, 312
MS, m/z 408 (M+,34%), 407 (20),406 (100), 376 StL: Hypogymnia physodes (1.) Nyl.
(15),375 (12),374 (40), 348 (24),347 (17), 346 TLC: A: 10, B: 31, B': 33, C: 19
(73), 321 (10),320 (ll), 319 (29), 318 (13), 306 HPLC: RI 18
(38),294 (17),293 (13),292 (54),291 (10), 290 MC: Figs. 44C,D; 45A,B
(13),281 (5),215 (4),213 (12), 211 (7),194 (27), Lit: C.F. Culberson 1969
187 (15), 164 (6), 83 (25),77 (8),67 (16),44 (4),
36 (6),28 (11)
Physodic acid (Physodsaure)
Deriv: 4-0-Methylphysciosporin, crystals, mp
244 (dec.), from physciosporin with CHzNz in CZ6H300S (470.50)
acetone at room temperature in 1 min
StL: Pseudocyphellaria Javeolata (Del.) Malme 7"
Me
TLC: A: 73, B': 59, C: 78, E: 37
Lit: Maass et al. 1977; Renner et al. 1978
Physodalic acid (Physodalsaure)

CZOHl601O (416.33)
#:
9 8'
Me 7 ~H2-0-COMe
6 1 eo-o 3 2' OH
5 4'
l' 7' Me
HO 4 3 0 5' 6' eOOH 5'"
CHO Me
8 9' Needles (MeOH-HzO), mp 205C (dec.)
React: KOH + NaOCI red, FeCl3 deep violet
Needles (acetone), mp 230-260 c (dec.) UV (MeOH): 212 (4.65), 263 (4.06), 314nm
React: KOH red-brown, PD orange, FeCl3 purple (3.49)
UV (MeOH): 212, 242, 318nm IR (KBr): 715, 748, 790, 812,858,892,1020, ll10,
IR (KBr): 670, 700, 720, 755, 780, 794, 842, 880, ll46, ll80, 1220, 1250, 1290, 1320, 1360, 1412,
940, 970, 1020, 1090, 1112, 1144, 1190, 1260, 1455, 1610, 1660, 1680,3000, 3300cm- 1
1350, 1390, 1410, 1430, ,1560, 1610, 1630, 1680, IH-NMR (90MHz,DMSO-d6): 0.86, 0.91 (2x3H,
1728, 3000, 3500 cm- 1 2xt, J=6Hz, Me-7", Me-Sill), 1.ll-1.24 (12H,
IH-NMR (400MHz,CDCI3-DMSO-d6): 1.52 (3H, m,6x-CH z-), 2.46 (2H,t,J=7Hz, -CHz-3"), 2.81
s,Me-COO-8'), 2.08 (3H,s,Me-9), 2.18 (3H,s, (2H,bs,-CH z-l"'), 3.97 (2H,s,-CH z-l"), 6.60,
Me-9'), 4.76 (2H,s,-CH z-8'), 6.26 (lH,s,H-5), 6.62 (2H) (3xs, H-3, H-5, H-3')
10.23 (lH,s,CHO-8) MS, m/z 427 (27%), 426 (100), 425 (5), 409 (5),
13C-NMR (50.29MHz,DMSO-d6): C-l: ll2.1, C- 408 (7), 383 (8), 370 (17),355 (10),249 (19),248
2: 164.0, C-3: ll1.8, C-4: 164.0, C-5: ll7.2, C-6: (34), 247 (13), 192 (20), 178 (15), 163 (9), 150
152.1, C-7: 160.7, C-8: 191.7, C-9: 21.2, C-l': (25), 124 (9), 123 (30), 121 (8),77 (4),69 (8), 55
ll5.8, C-2': 155.6, C-3': ll3.8, C-4': 145.7, C-5': (7),43 (13)
3.17 Depsidones 347
Deriv: Methyl physodate, prisms (EtOH-H 20), C-5': 141.73, C-6': 131.59, C-7': 170.94, C-8':
mp 15rC, from physodic acid with an equimo- 57.67, C-9': 14.78
lar amount of CH 2N2 MS, m/z 374 (M+,50/0), 357 (15), 356 (23), 340
13C-NMR (CDCIJ: C-1: 111.1, C-2: 161.2, C-3: (12), 330 (9), 313 (38), 312 (53), 299 (33), 298
105.7, C-4: 159.8, C-5: 116.9, C-6: 137.6, C-7: (14), 285 (29), 284 (32), 271 (26), 258 (84),257
161.2, C-l": 47.4, C-2": 208.4, C-3": 42.4, C- (27),244 (12), 243 (17),230 (65), 179 (51), 178
4": 22.9, C-5": 30.5, C-6": 22.2, C-7": 13.8, C-l': (32),165 (23), 164 (13), 151 (100), 150 (29), 138
108.2, C-2': 158.8, C-3': 106.3, C-4': 147.5, C-5': (19), 137 (16), 122 (16), 121 (12), 107 (15), 106
140.3, C-6': 139.8, C-7': 169.3, C-1"': 32.0, (28),85 (22),84 (36), 77 (34),65 (26),51 (64),50
C-2"': 31.0, C-3"': 28.0, C-4"': 22.2, C-5"': 13.9,7- (80)
COOMe: 51.9 Deriv: Pentaacetylprotocetraric acid, needles
StL: Hypogymnia physodes (1.) Nyl. (acetone), mp 113 DC, from protocetraric acid
TLC: A: 25, B: 35, B': 35, C: 18 with Ac 2 0-H 2S04
HPLC: Rj 25 StL: Flavoparmelia caperata (1.) Hale, Ramalina
MC: Pig. 44A,B farinacea (1.) Ach.
Lit: c.P. Culberson 1969; Jones et al. 1976 TLC: A: 3, B: 19, B': 19, C: 5, G: 29
HPLC: Rj 14
MC: Pig. 43C,D
Protocetraric acid (Protocetrarsaure)
Lit: c.P. Culberson 1969; Sala and Sargent 1981
ClsHl409 (374.29)
Psoromic acid (Psoromsaure)
9
Me ClsHl40S (358.29)
5~tO-O 9 7'
Me Me
HO~O 5h,~O-O
CHO
8
HO~O
Needles (acetone), mp 245-250 DC (dec.) CHO COOH
B 8'
React: KOH yellow, PD orange-red, heating with
EtOH-HCI blue-violet solution and blue-green Needles (acetone), mp 265 DC (dec.)
precipitate (Herberger's reaction) React: KOH yellow, NaOCI yellow, PD yellow,
UV (EtOH): 210, 238 (4.44), 312nm (3.68) PeCl3 wine red
IR (KBr): 680, 745, 785, 814, 840, 990,1020,1080, UV (MeOH): 211 (4.64),240 (4.58), S 271 (4.18),
1115, 1150, 1190, 1270, 1380, 1440, 1562, 1642, 317nm (3.59)
1738, 3000, 3500 cm- 1 IR (KBr): 670, 704, 748, 785, 808, 860, 888, 975,
IH-NMR (200MHz,acetone-d6 ): 2.47, 2.67 1010, 1058, 1125, 1150, 1178, 1200, 1220, 1260,
(2x3H,2xs,2x-Me), 4.81 (2H,s,-CH 2-8'), 6.75 1282, 1360, 1390, 1425, 1450, 1492, 1562, 1580,
(1H,s,H-5), 10.72 (1H,s,-CHO) 1645, l7.30, 3000, 3150, 3250, 3520cm-1
13C-NMR (acetone-d6 ): C-1: 112.9, C-2: 165.5, IH-NMR (270MHz,DMSO-d6 ): 2.18 (3H,s,Me-
C-3: 112.0, C-4: 163.9, C-5: 117.2, C-6: 152.5, 7'), 2.44 (3H,s,Me-9), 3.82 (3H,s,MeO-2'), 6.84
C-7: 161.79, C-8: 191.92, C-9: 21.72, C-l': (lH,s,H-5), 7.08 (IH,s,H-1'), 10.42 (1H,s,CHO-
116.29, C-2': 156.58, C-3': 112.9, C-4': 145.61, 8)
13C-NMR (25.05MHz,DMSO-d6 ): C-1:111.5, C- MS, m/z 388,370,354, 179

2: 164.4, C-3: 110.6, C-4: 163.9, C-5: 116.8, C-6: Deriv: Hexaacetylsalazinic acid, needles (ac-
152.4, C-7: 160.4, C-8: 193.7, C-9: 21.2, C-1': etone), mp 178C, from salazinic acid with
107.7, C-2': 154.5, C-3': 122.6, C-4': 143.0, C-5': Ac 2 0-H 2S04
142.3, C-6': 129.7, C-7': 9.2, C-8': 165.3, C-2- 13C-NMR (25.05MHz,CDCI3 ): C-1: 119.9 C-2:
OMe: 56.0 163.3, C-3: 117.9, C-4: 152.2, C-5: 124.6, C-6:
MS, m/z 358 (M-,5%), 357 (10), 343 (78), 330 147.1, C-7: 159.4, C-8: 84.1, C-9: 21.1, C-1':
(80),329 (40), 314 (90), 313 (100),299 (70),286 116.4, C-2': 145.4, C-3': 125.6, C-4': 148.6, C-5':
(90), 285 (100) 143.0, C-6': 136.8, C-7': 158.5, C-8': 55.0, C-9':
Deriv: Triacetylpsoromic acid, needles (EtOH), 90.4, Me-CO-: 20.2-20.8, Me-CO-: 167.8-170.1
mp 198-199C, from psoromic acid with Ac 2 0- StL: Parmelia saxatilis (1.) Ach.
H 2S04 TLC: A: 10, B: 7, B': 7, C: 4, G: 26
StL: Squamarina cartilaginea (With.) James HPLC: R, 5
TLC: A: 36, B: 41, B': 46, C: 41, G: 57 MC: Pigs. 45C,D; 46A,B,C
HPLC: R,21 Lit: c.P. Culberson 1969; Sundholm and Huneck
MC: Pigs. 42D; 43A.B 1981
Lit: c.P. Culberson 1969; Huneck and Sargent
1976; Sala and Sargent 1979; Sundholm and
Scensidin
Huneck 1981
Salazinic acid (Salazinsaure) Me ,

C1s H 12 0 IO (388.28) ~CO-::YC.
CI 3 OMe
Meo~
*
9 B' CI
Me CH 2 0H 3 0
Me
1 ~O-O I.' 3' OH
5 2' Needles (MeOH), mp 199-201 c
2 5' l' 0
HO 4 3 0 6' 7' IR (CHCI3 ): 1740cm-1
CHO HO 9' 0 IH-NMR (CDCI3 ): 2.49 (6H,s,2x-Me), 2.81, 3.91
B (2x3H,2xs,2x-OMe), 6.63, 6.67 (2x1H,2xs,H-3,
H-3')
Needles (acetone-H 2 0), mp 260-280C (dec.,
MS, m/z 372 (M+), 370, 368, 335, 199 (14%), 198
carbonization)
(13)
React: KOH yellow ~ deep red, but no separa-
StL: Diploicia canescens (Dicks.) Massal.
tionof crystals, PD orange, PeCl3 wine red
TLC: A: 75, B': 64, C: 88, E: 44
UV (MeOH): 212 (4.38), 238 (4.31), S 270 (3.91),
Lit: Mahandru and Tajbakhsh 1983; Elix and
317nm (3.57)
Ernst-Russell 1993
IR (KBr): 682, 730, 760, 800, 852, 870, 882, 920,
950, 1010, 1070, 1090, 1130, 1158, 1200, 1250,
1290, 1350, 1440, 1570, 1650, 1740, 2950, Siphulellic acid (Siphulellsaure)
3500cm-1
IH-NMR (60MHz,DMSO-d6 ): 2.45 (3H,s,Me-9), CI9HI4010 (402.30)
4.65 (2H,s,-CH 2-8'), 6.80 (1H,s,H-5), 6.85 (lH,s,
H-9'), 10.33 (1H,s,CHO-8)
3.17 Depsidones 349

7' Needles, mp 139-140 DC
Me co_*CH2~~~COM' IH-NMR (CDCI3 ): 1.00 (6H,t,J=9.8Hz,Me-3",
Me-Sill), 1.40-1.70 (8H,m,4x-CHc ), 2.86, 3.20
(2X2H,2xt,J=7.6Hz,-CH z-1",-CH z-1 111 ), 3.90
HO 1 (3H,s,-OMe), 6.59, 6.64 (2x1H,2xd,J=2.8Hz,H-
o
CHO COOH 3,H-5), 6.71 (1H,s,H-3')
8' MS, m/z 414 (M+,100%), 396 (43), 370 (60), 368
(40), 353 (27), 340 (67), 325 (27), 3ll (37), 297
Microcrystals (acetone), mp > 240 DC (dec.)
(20),285 (30), 272 (23),269 (17), 257 (20),245
React: PD yellow
(20),219 (13), 193 (57), 178 (33)
IH-NMR (CDCI3 -acetone-d6 ): 2.03 (3H,s,-OAc),
StL: Cladonia grayi Merr. ex Sandst.
2.56, (3H,s,-Me), 5.29 (2H,s,-CH z-7'), 6.71, 7.65
TLC: Rp A: 0.39, B: 0.67, C: 0.52
(2X1H,2xs,H-5,H-1'), 12.40 (2H,bs,-OH)
HPLC: R[ 35
13C-NMR: C-1: ll1.16, C-2: 153.86, C-3: ll7.76,
Lit: C.F. Culberson et al. 1985; Elix et al. 1987f
C-6: 165.38, C-7: 161.27, C-8: 195.58, C-9: 20.79,
C-1': ll4.37, C-2': 154.05, C-3': ll9.62, C-4':
142.03, C-7': 56.30, -CO-Me: 171.25, -CO-Me: Stictic acid (Stictinsaure)
22.25
Cl9Hl409 (386.30)

MS, mlz 342 (1 %),298 (1), 179 (1), 152 (28), 151
(33), 129 (6), III (10),98 (17), 83 (19),60 (50)
9 8'
Deriv: Acetylsiphulellic acid, needles (CHzClz- Me 7 M~
n-pentane), mp 184-186 DC, from siphulellic 5 6 1 CO-O I..' 3 2 , OH
acid with AC zO-HzS0 4
StL: Siphulella coralloides Kantvilas, Elix et 2 s' '0
MeO 4 3 6' 7'
James o 0
CHO HO 9'
TLC: A: 12, B': 24, C: 8, G: 38 8
HPLC: R[ 10
Lit: Kantvilas et al. 1992; Elix et al. 1993c
Needles (acetone-H 20), mp 270-272 c (dec.)
React: KOH deep yellow ~ brownish, PD or-
Stenosporonic acid (Stenosporonsaure) ange, FeCl3 purple
UV (MeOH): 213 (4.60), S 237 (4.47), S 270,
'
C23 H z6 0 7 (414.44) (4.10),313 nm (3.77)
IR (KBr): 792, 900, 978, 1022, 1085, llOO, ll50,
3" 1230, 1262, 1300, 1390, 1440, 1468, 1550, 1600,
Me 1680, 1700, 1730,3000, 3450cm-1
1" IH-NMR (270MHz,DMSO-~): 2.19 (3H,s,Me-8'),
2.49 (3H,s,Me-9), 3.91 (3H,s,MeO-4), 6.61 (lH,
5 CO-O
s,H-9'), 7.10 (1H,s,H-5), 10.46 (lH,s,CHO-8)
I3C-NMR (25.05MHz,DMSO-d6 ): C-1: ll3.0, C-
MeO 3 0
2: 1665, C-3: ll4.4, C-4: 162.5, C-5: ll2.7, C-6:
151.0, C-7: 160.7, C-8: 186.6, C-9: 21.7, C-4-
OMe: 56.8, C-1': 109.1, C-2': 152.0, C-3': 120.8,
Me C-4': 148.0, C-5': 137.4, C-6': 135.8, C-7': 163.0,
5'" C-8': 9,7, C-9': 95.5
MS, m/z 386 (M+,57%), 368 (27), 342 (20), 341 Substictic acid (Substictinsaure)
(29), 340 (27), 325 (8), 314 (25), 313 (16), 312

(18), 297 (9), 285 (18), 259 (22), 258 (17), 257 ClsHl209 (372.28)
(20), 231 (15), 230 (25), 193 (75), 191 (49), 166 9
(20),165 (15),164 (15),115 (15),91 (31),90 (25), Me 7 '
89 (39), 83 (100),77 (56), 67 (43), 65 (40), 63 (50), 5 6 1 CO-~/
3 2' OH
55 (38),53 (55),51 (63),44 (93) 2 5' '0
Deriv: Tetraacetylstictic acid, plates (acetone- MeO 4 3 0 6' 7'
H 20), mp 221-222C, from stictic acid with CHO HO S' 0
Ac 2 0-H 2S0 4 8
StL: Lobaria retigera (Bory) Trev., Stereocaulon
vesuvianum Pers. Microcrystals (acetone-n-pentane), mp > 270C
TLC: A: 32, B: 9, B': 9, C: 18, E: 0, F: 0, G: 34 (dec.)
HPLC: R] 6 React: PD orange
MC: Figs. 46B, C IH-NMR (200MHz,CDCI3 -DMSO-d6 ): 2.54 (3H,
Lit: C.F. Culberson 1969; Sundholm and Huneck s,Me-9), 3.96 (3H,s,4-0Me), 6.67 (lH,s,H-8'),
1981 6.69 (IH,s,H-5), 7.11 (lH,s,H-3'), 10.66 (1H,s,
CHO-8
13C-NMR (50.1 MHz,DMSO-d6 ): C-2: 167.1, C-4:
Subnotatic acid (Subnotatsaure)
163.1, C-5: 111.9, C-6: 150.0, C-8: 187.4, C-9:
C17H I4 0 7 (330.07) 22.1, C-4-0Me: 56.6, C-l': 107.0, C-2': 151.3,
C-3': 110.3, C-8': 96.5
X< O~COOH
MS, m/z 372 (M+,100%), 354 (27), 344 (12), 328
Me / (35), 326 (49), 300 (45), 298 (27), 243 (21), 230
5 CO-O 3 OH (43), 193 (53), 191 (48)
StL: Aspicilia mashiginensis (Zahlbr.) Oxner
M.O , TLC: A: 13, B': 4, C: 10, G: 23
Me Lit: Elix et al. 1987b
Flakes (acetone-cyclohexane), mp 223-225C Succinprotocetraric acid

(dec.) (Succinprotocetrarsaure)
IH-NMR (CDCIJ: 2.48, 2.73 (2x3H,2xs,2x-Me), C22 H I8 0 12 (474.36)

3.91 (3H,s,-OMe), 6.61 (2H,s,H-3,H-5), 6.75
(IH,s,H-3'), 10.91 (2H,bs,-OH,-COOH) 8' 1/1 31' /1
MS, m/z 330 (M+,6%), 315 (5),286 (13),272 (3), Me ~CH2-0-CO'- /'- ~OOH
214 (13), 186 (17), 165 (25), 151 (12), 150 (100), 5 CO-O O H ; ; : '-
108 (44), 96 (19),91 (31),83 (34),80 (30), 77 (30),
71 (37),69 (37), 52 (75) HO COOH
o
Deriv: Methyl subnotate, prisms (EtOAc-n-pen- CHO Me
tane), mp 196-19rC, from subnotatic acid with
CH 2 N2 at OC in 1 min Needles (acetone-H20), mp 240-242C (dec.)
StL: Xanthoparmelia notata (Kurok.) Hale React: PD yellow-orange
TLC: A: 25, B': 37, C: 36, G: 48 UV (MeOH): 212 (4.54),240 (4.38), S 272 (3.97),
Lit: Elix and Lajide 1984a 313nm (3.71)
3.17 Depsidones 351
IR (Nujol): 1655, 1690, 1728, 1740cm-1 (17),269 (10),259 (7),258 (7), 257 (12),242 (10),
IH-NMR (60MHz,DMSO-d 6 ): 2.52 (10H,m,Me- 241 (14),202 (14), 201 (24),200 (7), 196 (10), 195
9,Me-9',-CHz-2", CH2-3"), 5.26 (2H,s,-CH 2- (12), 164 (26), 163 (10), 157 (14), 152 (7), 151
8'), 6.91 (1H,s,H-5), 10.71 (IH,s,CHO-8) (59),150 (10), 147 (7),145 (10), 143 (14), 141 (7),
MS, m/z 358 (1%),356 (I), 314 (2),258 (2), 230 135 (24), 134 (36), 129 (10), 128 (7), 127 (10), 124
(1),186 (5), 134 (3), 106 (2), 101 (8),100 (24),74 (14), 122 (14), 121 (10), 120 (10), 115 (20), 108
(23),73 (21), 72 (8),71 (2),69 (2), 57 (3), 56 (9), (10),107 (20), 106 (69), 105 (20)
55 (33),54 (2), 46 (4),45 (33),44 (100),43 (9) Deriv: Diacetylvariolaric acid, rhombic crystals
Deriv: Succinic acid, crystals (H 20), mp 185 c, (MeOH), mp 245-246C, from variolaric acid
by heating of succinprotocetraric acid at 150 CI with ACzO-H zS0 4
0.1 mm for 10 min in a sublimator StL: Ochrolechia parella (1.) Mass., Pertusaria
StL: Chondropsis semiviridis (Nyl.) Nyl., lactea (1.) Am.
Relicina sublimbata (Nyl.) Hale, Xantho- TLC: A: 18, B: 13, B': 12, C: 14
parmelia reptans (Kurok.) Hale HPLC: Rl 3
TLC: A: 4, B: 23, B': 18, C: 10, G: 26 Lit: c.P. Culberson 1969; Sundholm and Huneck
HPLC: RJ 10 1981; Rana et al. 1975; }ongen et al. 1979
Lit: Baker et al. 1973
Vesuvianic acid (V esuviansaure)
Variolaric acid (Variolarsaure)

C16H IO 0 7 (314.24)
8
sMe1 to-~o
4' 3' 2' 8'
4 2 5' 0
HO 3 S' l' 7'
o 0
OH
Needles (80% aqueous acetone), mp 296C (dec.) Crystals (EtOAc), mp 245C

React: PeCl3 purple React: PD yellow
UV (MeOH): 224 (4.83), 250 (4.39), S 278 (4.21), UV (EtOH): 237, S 260, 297nm
333nm (4.00) IR (KBr): 1080, 1130, 1220, 1300, 1604, 1700,
IR (KBr): 680, 690, 720, 730, 760, 775, 792, 870, 1730, 1745, 3400cm- 1
890, 1000, 1010, 1085, 1130, 1144, 1160, 1200, IH-NMR (400MHz,CDCIJ: 1.29 (3H,t,}=7Hz,-
1275, 1320, 1342, 1382, 1464, 1490, 1510, 1578, O-CH 2 -Me), 2.30, 2.57 (2X3H,2xs,Me-9,Me-8'),
1620,1720, 1744,3000, 3500cm-1 3.98 (3H,s,MeO-4), 4.01 (2H,q,}=7Hz,-O-
IH-NMR (60MHz,DMSO-d 6 ): 2.36 (3H,s,Me-8), CH 2 - ) , 6.49 (IH,s,H-5), 7.92 (1H,s,H-9'), 10.54
5.21 (2H,s,-CH z-8'), 6.64 (2H,d,}=3Hz,H-3,H- (1H,s,CHO-8)
5),6.96 (1H,s,H-3') 13C-NMR (100.6MHz,CDCI3): C-l: 114.8, C-2:
13C-NMR (25.05MHz,DMSO-d6 ): C-l: 115.4, C- 160.6, C-3: 107.9, C-4: 163.6, C-5: 111.9, C-6:
2: 153.9, C-3: 112.2, C-4: 159.7, C-5: 122.9, C-6: 151.4, C-7: 169.7, C-8: 186.6, C-9: 22.3, C-4-
144.6, C-7: 159.9, C-8: 20.9, C-l': 117.9, C-2': OMe: 56.6, C-l': 114.2, C-2': 152.4, C-3': 120.9,
145.4, C-3': 113.0, C-4': 139.5, C-5': 142.2, C-6': C-4': 147.3, C-5': 132.2, C-6': 123.1, C-7': 189.1,
149.4, C-7': 166.5, C-8': 69.3 C-8': 9.1, C-9': 102.1, C-2' -O-.GH2-: 66.7, C-2'-
MS, m/z 314 (M+,100%), 286 (21), 285 (7), 270 O-CHz-Me: 14.9
MS, m/z 414 (M+,950/0), 370 (11), 369 (42), 368 Needles (dioxane-acetone), mp 245-247C
(100),341 (15),340 (30), 312 (16), 287 (16), 285 React: KOH weak yellow, PD yellow, FeCl3
(11),210 (19), 191 (11),58 (33),43 (56) (EtOH) wine red
StL: Stereocaulon alpinum Laur. (probably an UV (MeOH): 212, 240 (4.47), 308nm (3.68)
artefact) IR (KBr): 704, 743, 781, 794, 833-843, 881, 1015,
Lit: Solberg 1977; Ingolfsdottir et al. 1986 1121, 1149, 1198, 1242, 1266, 1305, 1348, 1389,
1422, 1543, 1613, 1639, 1724, 2985, 3333-
3509cm-1
Vicanicin
IH-NMR (CDCl3 ): 2.24, 2.52, 2.70 (3x3H,3xs,3x-
Me), 6.70 (1H,s,H-5), 10.76 (IH,s,CHO-8).
MS, m/z 358 (M+,1000/0), 341 (15),340 (52),314
(17), 313 (21), 312 (87), 311 (13), 286 (9), 285
CI*Me
co_=*Me OMe (29), 284 (23), 283 (10), 273 (10), 272 (51), 259
(14),258 (63),257 (25),256 (30), 245 (25),230
HO CI (20),209 (10),207 (12), 180 (14), 179 (38), 177
o (26),170 (17), 152 (11), 151 (9), 150 (9),134 (10),
Me Me
131 (9), 106 (26), 105 (21)
Needles (benzene), mp 248-250C Deriv: Methyl virensate, fiat needles (EtOAc),
React: FeCl3 (EtOH) - mp 215-216C, from virensic acid with dim-
UV (MeOH): 270 (3.94), S 324nm (2.48) ethyl sulphate and NaHC0 3 in acetone
IR (Nujol): 730, 755, 770, 850, 900, 970, 980, StL: Bryoria tortuosa (Merr.) Brodo et D.
1020, 1090, 1150, 1220, 1300, 1310, 1350, 1400, Hawksw.
1420, 1480, 1600, 1750, 2900, 3500cm~1 TLC: A: 26, B: 57, B': 56, C: 38, G: 56
IH-NMR (90MHz,CDCl3-DMSO-d6): 2.24, 2.41, HPLC: RI 9
2.45,2.59 (4x3H,4xs, 4x-Me), 3.75 (3H,s,-OMe) MC: Figs. 46D; 47 A,B
MS, m/z 386 (M+), 384, 382, 349, 347 Lit: Aghoramurthy et al. 1961; C.F. Culberson
Deriv: Acetylvicanicin, rectangular prisms 1969; Sala and Sargent 1981; Pulgarin and
(AcOH), mp 213-214C, from vicanicin with Tabacchi 1989
Ac 2 0-H 2 S0 4
StL: Teloschistes flavicans (Sw.) Norm.
TLC: A: 67, B: 75, B': 77, C: 64, E: 52 Vittatolic acid (Vittatolsaure)
HPLC: R] 37 C26H3009 (486.50)
Lit: Dyer et al. 1967; C.F. Culberson 1969;
7 '1
Sargent et al. 1976; Quilhot et al. 1983 Me
Virensic acid (Virenssaure)

C1sH]40S (358.29)
Me eo-X
Mex OH
HO eOOH
o
CHO Me
Me
5111
3.18 Depsones 353
Needles (MeOH-H 20), mp 178C (dec.), [aJbc m,-CH 2-1"'), 3.64 (3H,s,-OMe), 5.82 (1H,s,H-
11 (EtOH, c 1.0) 3), 6.39 (1H,s,H-5), 6.70 (1H,s,H-3'), 7.00 (1H,
React: FeCl3 (EtOH) violet bs,-COOH), 12.20 (1H,s,-OH)
IR (KBr): 1610, 1663, 1704, 3068, 3413 cm- 1 MS, m/z 470 (M+,5%), 426 (4), 105 (13),88 (19),
IH-NMR (90MHz,CD 30D): 0.96 (6H,t,Me- 70 (51),61 (100)
7",Me-5"'), 1.16-2.00 (10H,bs,5x-CH 2 -), 2.66 StL: Pertusaria truncata Krempelh.
(2H,d,J=7Hz,-CH 2-3"), 3.13 (2H,bs,-CH 2-1"'), TLC: RFA: 0041, B: 0049, C: 0040
4.0 (1H,bs,H-4"), 4.01 (2H,s,H-1"), 6.50 HPLC: Rj 44.5
(lH,d,J=2Hz,H-3'), 6.60 (2H,bs,H-3,H-5) Lit: Elix et al. 1994d
MS, m/z 486 (M+), 442
Deriv: Triacetylvittatolic acid, mp 146-147C
Isohyperpicrolichenic acid
[aJb4 + 1.0 (EtOH, c. 1.0), from vittatolic acid
(Isohyperpikrolicheninsaure)
with Ac2 0-H2 S0 4
StL: Hypogymnia vittata (Ach.) Ras. C26H340S (426.53)
TLC: A: 8, B': 21, C: 5, G: 32
HPLC: Rj 19
Lit: Hirayama et al. 1975, 1976b
3.18
Oepsones
Hyperpicrolochenic acid OH
(Hyperpikrolicheninsaure)
COOH
C27H3407 (470.54)
M~
5'"
Crystals (n-hexane-CH 2CI 2), mp 105-107.5C

IH-NMR (CDCI3 ): 0.84-0.86 (6H,m,Me -7",Me---:
5"'), 1.20-1.52 (16H,m,-CH 2-2",-6"-CH2-2"'-
4"'),1.86 (2H,t,J=7.3Hz,-CH 2-1"), 2044, 2.86 (2H,
m,-CH 2-1"'), 3.67 (3H,s,-OMe), 5.85 (lH,s,H-
3), 6042 (lH,s,H-5), 6.76 (lH,s,H-3'), 7.00 (lH,
bs,-COOH), 12.19 (1H,s,-OH)
MS, m/z 426 (M+,7%), 69 (57), 55 (100)
StL: Pertusaria truncata Krempelh.
M~
7'" TLC: RF A: 0.39, B: 0.47, C: 0.38
HPLC:'Rj 46
Crystals (n-hexane-CH 2CI 2 ), mp 95-97C Lit: Elix et al. 1994d
IH-NMR (CDCIJ: 0.82-0.91 (6H,m,Me-5",Me-
7"'), 1.17-1.46 (16H,m,-CH 2-2"-4",-CH 2-2"'-
6"'), 1.84 (2H,t,J=7 Hz,-CH 2-1"), 2043, 2.83 (2H,
Isomegapicrolichenic acid
(Isomegapikrolicheninsaure)
C31H4207 (526.65)
9"
OH
M~
COOH
M~
3 111
Crystals (cyclohexane-toluene), mp 160-162C
OH (dec.)
IH-NMR (CDCIJ: 0.75-0.88 (6H,m,Me-5",Me-
o 3"'), 1.27-1.28 (8H,m,-CH 2-2"-4",-CH 2-2"'),
2.14 (4H,m,-CH 2-1",-CH 2-1"'), 3.69 (3H,s,-
OMe), 5.85, 6.43 (2xlH,2xs,H-3,H-5), 6.87
(1H,s,H-3')
MS, m/z 414 (M+,I%), 380 (1), 378 (4),370 (7),
311 (5), 299 (3), 283 (12), 257 (8), 256 (5), 255
(27), 57 (100)
StL: Pertusaria amara (Ach.) Nyl.
Crystals (n-hexane-CH2CU, mp 145C TLC: RF A: 0.34, B: 0.37, C: 0.34
IH-NMR (CDCI3): 0.84-0.90 (6H,m,Me-9",Me- HPLC: Rr 4.89min
7"'), 1.22-1.44 (24H,m,-CH 2-2" -8",-CH 2-2"'- Lit: Elix et al. 1991c, 1994d
6"'),1.90 (2H,t,J=7.2Hz,-CH 2-1"), 2.46, 2.90 (2H,
m,-CH 2-1"'), 3.70 (3H,s,-OMe), 5.98 (1H,s,H- Megapicrolichenic acid
3), 6.50 (1H,s,H-5), 6.77 (1H,s,H-3'), 7.00 (1H, (Megapikrolicheninsaure)
bs,-COOH), 12.20 (1H,s,-OH)
MS, m/z 526 (M+,5%), 483 (11), 482 (41), 355 C31H4207 (526.65)
(10),339 (8),241 (10),57 (69), 55 (100)
TLC: RF A: 0.44, B: 0.62, C: 0.44
HPLC: Rj 55
Isosubpicrolichenic acid
(Isosubpikrolicheninsaure)
C23H2607 (414.44)
Me
gill
3.18 Depsones 355
Crystals (n-hexane), mp 116-11rC MeO-2), 5.92 (1H,s,H-3), 6.31 (lH,s,H-5), 6.76

IH-NMR (CDCI3 ): 1.19-1.44 (6H,m,Me-7",Me- (1H,s,H-3')
9"'), 1.19-1.44 (24H,m,-CH 2-2"-6",-CH2-2"'- !3C-NMR (25.05MHz,CDCI3): C-1: 59.1, C-2:
8"'), 1.88 (2H,t,J=7.2Hz,-CH 2-1"), 2.44, 2.88 171.9, C-3: 103.2, C-4: 188.2, C-5: 127.1, C-6:
(2H,m,-CH 2-1"'), 3.69 (3H,s,-OMe), 5.98 (lH, 154.3, C-7: 170.1, C-1": 32.2, C-2": 31.1, C-3":
s,H-3), 6.50 (IH,s,H-5), 6.75 (lH,s,H-3'), 7.00 30.9, C-4": 22.3, C-5": 13.9, C-2-0Me: 56.6, C-
(IH,bs,-COOH), 12.20 (1H,s,-OH) 1': 108.5, C-2': 166.9, C-3': 99.0, C-4': 158.3, C-
MS, m/z 526 (M+,36%), 498 (4),483 (7),482 (24), 5': 116.3, C-6': 145.6, C-7': 173.4, C-l"': 31.7,
57 (56), 55 (100) C-2"': 30.7, C-3"': 26.3, C-4"': 22.1, C-5 11f : 13.7
StL: Pertusaria truncata Krempelh. MS, m/z 442 (M-,5%), 441 (4), 415 (50), 414
TLC: Rp A: 0.46, B: 0.65, C: 0.46 (100), 386 (18), 365 (18)
HPLC: R] 53 Deriv: Methyl picrolichenate, needles (MeOH),
Lit: Elix et al. 1994d mp 102-103.5 c, from picrolichenic acid with
an equimolar amount of CH 2 N 2 in Et2 0 at 0 c in
1 min
Picrolichenic acid (Pikrolicheninsaure)
CZSH3007 (442.49) TLC: A: 38, B: 39, B': 45, C: 36
HPLC: R] 22
II
5 MC: Fig. 47C
Me Lit: Wachtmeister 1958; Sundholm and Huneck
1981
Subpicrolichenic acid (Subpikrolicheninsaure)

C23 H 26 0 7 (414.44)
3 11
Me
Me
5"1 OH
Prisms (benzene), mp 184-187C (dec.), inten- 0 eOOH

sively bitter taste
React: KOH + NaOCI red, FeCl3 (EtOH) violet
UV (MeOH): 220 (4.83), 242 (4.66), 280nm
(4.14) Me
5111
IR (KBr): 682, 762,800,848,892,932,1008,1030,
1064, 1100, 1125, 1155, 1170, 1222, 1290, 1380, Needles (cyclohexane-toluene), mp 164-165C
1450, 1590, 1660, 1808, 2600, 2650, 2690, 2698, lH-NMR (CDCU: 0.80-0.87 (6H,m,Me-3",Me-
3450cm-1 5"'), 1.16-1.26 (8H,m,4x-CH 2-), 2.18 (4H,m,-
lH-NMR (270MHz,DMSO-d 6): 0.75 (3H,t,Me- CH 2-1",-CH 2-1"'), 3.65 (3H,s,MeO-2), 5.82
5"), 0.78 (3H,t,Me-5"'), 1.11 (8H,m,4x-CH z-), (1H,s,H-5), 6.40 (1H,s,H-3), 6.70 (1H,s,H-3')
1.34 (4H,m,-CH 2-2",-CH 2-2"'), 1.79 (2H,t,- MS, m/z 414 (M+,4%), 396 (8), 370(4), 356 (3),
CH 2-1"), 2.14,2.39 (2H,t,-CH z-1"'), 3.64 (3H,s, 344 (12), 337 (5), 311 (7),281 (IO), 260 (17),233
(29),217 (6),165 (4),149 (13), 142 (7), 113 (15), 3.19

99 (23), 83 (26),69 (40), 57 (69),43 (100) Naphthopyranes
TLC: RF A: 0.33, B: 0.36, C: 0.33 Simonyellin
HPLC: RI 15
Lit: Elix et al. 1991c C l4 H lO 0 6 (274.22)
Superpicrolichenic acid
(Superpikrolicheninsaure)
C29 H 3s0 7 (498.59)
Me 0
HO
W
4
5
6
o
0109
7
Me
OH
Fluffy yellow crystals (Et2 0), mp 274-275C,

softening between 240-268 c
IH-NMR (300MHz,CDCI3 ): 2.90 (3H,s,-Me),
4.22 (3H,s,-OMe), 7.01 (2H,s,H-3,HO-5), 7.99
(lH,s,H-8), 11.36 (lH,s,HO-9)
MS, m/z 274 (M+,96%), 259 (9),256 (14), 246 (5),
245 (23),232 (12),231 (100),230 (18),229 (10),
228 (60),203 (7),202 (6),200 (10), 185 (27), 175
(10), 174 (12), 172 (9), 160 (6), 150 (5), 149 (9),
148 (5),147 (30),146 (8),145 (6), 144 (5),131 (7),
129 (8), 123 (8), 121 (5), 119 (19), 118 (24), 117
(12), 116 (5), 115 (10), 114 (5), 113 (6), 111 (6),
109 (6), 107 (5), 105 (6), 103 (13), 102 (12), 101
(16)
Deriv: Simonyellin tetraacetate, mp 200-201 c
(CHCI 3-cyclohexane), from simonyellin with
Needles (cyclohexane), mp 108-110C Ac2 0-Py at room temp. in 24h.
IH-NMR (CDCI 3 ): 0.84-0.90 (6H,m,Me-7",Me- StL: Simonyella variegata Steiner
7111 ), 1.16-1.28 (20H,m,10x-CH 2-), 2.20 (4H,m,- HPLC: RI 11.40
CH 2-1",-CH 2-1 111 ), 3.68 (3H,s,MeO-2), 5.87 (lH, Lit: Follmann and Huneck 1969; Elix et al.
s,H-5), 6.44 (1H,s,H-3), 6.76 (1H,s,H-3'), 12.15 1995b; Elix, pers. comm. to S. Huneck, 26.6.1995
(s,-OH)
MS, m/z 498 (M+,7%), 470 (46), 452 (14), 440 3.20
(44),426 (35),412 (10),399 (7), 383 (18),357 (9),
Terpenoids
325 (5),273 (6),247 (5), 232 (11),218 (100),203
(58), 189 (56), 173 (25), 161 (35), 135 (43), 109
3.20.1
(31),95 (45), 81 (3),69 (42), 55 (39)
Monoterpenoids
TLC: RF A: 0.54, B: 0.57, C: 0.53
Borneol
HPLC: RI 34
3.20 Terpenoids 357
EB/OH
Me (-)-Carvone [(-)-Carvon]
C JO H I40 (150.21)
Me
(-)-borneol
Hexagonal plates with a camphoraceous odour,
mp 208C, [an - 37.8 (benzene)
StL: Evernia prunastri (1.) Ach. Me
Lit: Gavin and Tabacchi 1975; Gavin et al. 1978
Oil, bp 230-231 DC, [an - 62
Camphene (Camphen) MS, m/z 150 (M+), 135, 108,93, 82, 58, 54
CJOH I6 (136.23) Lit: Solberg 1986
C[t~
1,8-Cineol
CJOH I8 0 (154.24)
(-) -camphene
Crystals, mp 51C, bp 17 52C, [aU! - 103;9
p-\-Me
Me~
Viscid oil with a characteristic camphoraceous
odour, mp 1C, bp 1563 DC, nbO 1.4575
Camphor (Campher) StL: Evernia prunastri (1.) Ach.
CJO H I6 0 (152.23) Lit: Gavin and Tabacchi 1975; Gavin et al. 1978
p-Cymene (p-Cymol)
CJOH I4 (134.21)
(-)-camphor
Crystals with a very characteristic odour, mp
178.5-179C, [a]bO - 41.4 (abs. EtOH)
Oil, bp 177 DC, nbo 1.4904
Fenchol Oil, bp 198-199C, [a]D - 20.7, nbo 1.4668

ClOH1SO (154.24)
HO~ Myrcene (Myrcen)
MeW C lOH 16 (136.23)
Me Me
(+) -a-fenchol (+ )-B-fenchol

Crystals, mp 48C, Crystals, mp 5C,
[ana + 11 (EtOH) [anD + 24 (EtOH)

Lit: Gavin and Tabacchi 1975; Gavin et al. 1978 Oil with a pleasant odour, bp 166-168C, nf?
1.4700
Limonene (Limonen) Lit: Gavin and Tabacchi 1975; Gavin et al. 1978
C lO H 16 (136.25)
a-Pinene (a-Pinen)
ClO H 16 (136.23)
o
Me
(-)-limonene
(-)-a-pinene
Oil, bp 176-176.4C, [ana - 126.8
StL: Evernia prunastri (1.) Ach. Oil, bp 155-156C, [a]D - 48.3, ng; 1.4685
Lit: Gavin and Tabacchi 1975; Gavin et al. 1978 StL: Evernia prunastri (1.) Ach.
Linillool
ClOH1SO (154.24) B-Pinene (B-Pinen)
C lO H 16 (136.23)
~
~
(-)-linalool (-)-B-pinene
3.20 Terpenoids 359
0y
Oil, bp 163-164 DC, [a]O - 22, ni> 1.4782 Me
Terpinen-4-o1 Me~Me
ClO H l8 0 (154.24)
(+ )-a-thujone
Oil, bp 199-201C, [a]b8 + 20, nfi 1.4490
Lit: Gavin and Tabacchi 1975; Gavin et aI. 1978
Me~Me ~- Thujone, iso-Thujone (~- Thujon, iso-Thujon)
(+)-terpinen -4-01 C lO H l6 0 (152.23)
Oil, bp 209-212 DC, [a]o + 25.2, n~ 1.4785

a-Terpineol
0t5
Me~Me
ClO H l8 0 (154.24)
(- )-~-thujone
Oil, bp 201-202 DC, [am - 77.3, nb4 1.4540

3.20.2
Sesquiterpenoids
(+ )-a-terpineol
Fukinanolide A, Bakkenolide A
Crystals, mp 38-40C, [a]o + 95.9, nb8 1.4832 (Fukinanolid A, Bakkenolid A)
StL: Evernia prunastri (1.) Ach. C1s H 22 0 2 (234.33)
Qfo /~
a-Thujone (a-Thujon)
H
C lO H l6 0 (152.23)
Me
Crystals (n-pentane), mp 80.5-80.6 DC, [aW + 17

(MeOH, c 1.0)
MS, m/z 234 (M+), 219, 124, 111 OH

StL: Cetraria islandica (1.) Ach. Me
Lit: Solberg 1986; Shirahata et al. 1969
3.20.3
Diterpenoids
Me
Me
(-)-ent-Kauran-16a-ol
Crystals (EtOH), mp 53C, bpo.z 144-145 c, [all?
CZO H 34 0 (290.47)
+ 30.4 (EtOH)
IR (Nujol): 675, 735, 888, 9l3, 988, 1037, 1101,
1115, 1138, 1190, 1202, 1222, 1254, 127l, l315,
l345, 1409, 1643, 3390 cm-l
StL: Letharia vulpina (1.) Hue
Lit: Grant 1959; Tabacchi and Tsoupras 1987
Needles (MeOH), mp 216-21rC, [an - 64.2 Phytol

(CHCI 3, c 1.00)
IR (KBr): 685, 730, 750, 762, 784, 824, 862, 884,
936, 970, 1000, 1010, 1038, 1068, 1112, 1124, Me Me Me
1160, 1180, 1200, 1215, 1260, 1290, l340, l370, Me
l390, 1450, 1470,3000, 3400cm- 1
lH-NMR (60 MHz,CDCI3 ): 0.80, 0.83, 1.00, 1.32 Oil, bpo.oz l32C, [ans + 0.2
(4x3H,4xs,4x-Me) StL: Letharia vulpina (1.) Hue
MS, m/z 290 (M+,22%), 275 (10), 273 (23), 272 Lit: Tabacchi and Tsoupras 1987
(100),257 (36),232 (60), 217 (20), 148 (23), 147
(22), l37 (36), 134 (37), 125 (20), 123 (50), 119
Rimuene (Rimuen)
(20),109 (30),105 (30), 95 (40),94 (28), 81 (37),
69 (45), 55 (36),43 (50),41 (40)
Deriv: Acetyl-(-)-ent-kauran-16a-ol, flat nee-
dles (n-hexane), mp 141-143C, from (-)-ent- Me
kauran-16a-ol with ACzO-pyridine at 100C in ..... ~CH2
2h
StL:.Ramalina tumidula, (Tayl.) Hun. et Follm.
MC: Fig. 54B,C
Lit: Huneck and Follmann 1965; Lehn and Me ....
Huneck 1965 Me
Needles (EtOH), mp 55C, [a]D + 44.7, + 56
Manool (CHCI3)
IR: 820, 856, 909, 998, 1408, 1635, 3082 cm- 1
CZO H 34 0 (290.47) lH-NMR (60 MHz,CDCI 3): 0.96, 0.97, 1.01,
1.07 (4x3H,4xs,4x-Me), 4.87-6.27 (3H,m,-CH=
CH z), 4.55 (1H,m,H-6)
3.20 Terpenoids 361
StL: Evernia prunastri (1.) Ach. Crystals, mp 220-222C, [am - 86.5 (EtOH),
Lit: Connolly et al. 1966; Corbett and Wyllie [aJbB - 99.2 (CHCI3)
1966; Nicollier 1979 UV: 242nm (3.91)
IR (KBr): 1608, 1662cm-1
lH-NMR (CDCI3 ): 0.78 (3H,d,J=6.6Hz), 0.83
(-)-Sandaracopimaric acid
(3H,s), 0.88 (3H,d,J=6,7Hz) 0.99 (6H,s,d,J=
[(- ) -Sandaracopimarsaure]
6.2Hz), 1.00-1.92 (19H,m), 2.37 (lH,dd,Jl=14.6,
C2oH3002 (302.44) J2=6.9 Hz), 2.47 (lH,dd,J 1=11.5,J2=6.3 Hz), 3.33
(lH,d,J=16.0.0,J2=3.5 Hz), 8.69 (lH,s)
MS, mlz 370 (M+), 325
Deriv: Retigeranic acid A p-bromoanilide, mp
276-278C, [am - 56.2, from retigeranic acid A
chloride with p-bromoaniline
StL: Lobaria isidiosa (Miill.Arg.) Vain.
TLC: A: 73, Bf: 95, C: 83, E: 81; RF 0.54 (n-
hexane: EtOAc = 4: 1)
Lit: Kaneda et al. 1972, 1974; Corey et al. 1985;
Needles (n-hexane), mp 163-164.5 c, [ans + 19 Paquette et al. 1987; Wright et al. 1988; Hudlicky
(CHCI3, c 0.46) et al. 1989; Wender and Singh 1990; Sugawara et
IR (CHCI3): 850, 860, 920, 1000, 1695, 2500- al. 1991
3600cm-1
lH-NMR (200MHz,CDCI3): 0.83, 1.04, 1.20
Retigeranic acid B (Retigeransaure B)
(3x3H,3xs,3x-Me), 4.89 (lH,d,J=1O.6Hz,H-16),
4.90 (lH,d,J=17.4Hz,H-16), 5.22 (lH,s,H-14), C2sH3S02 (370.55)
5.77 (lH,dd,J=10.6 and 17.4Hz,H-15)
MS, mlz 302 (M+,12%), 287 (21), 274 (5), 257
(100), 119 (36), 107 (37), 105 (42)
StL: Ramalina hierrensis Krog et 0sth.
Lit: Gonzalez et al. 1992b
Me
3.20.4
Sesterterpenoids Crystals, mp 188-189C, [am - 30.4 (EtOH)
MS, m/z 370 (M+)
Retigeranic acid A (Retigeransaure A) StL: Lobaria isidiosa (Miill.Arg.) Vain.
Lit: Sugawara et al. 1991
C2sH3S02 (370.55)
17
18;.
Me--<z.9
24 Me
25
3.20.5
Triterpenoids '" ,c-Me
"'1 'OCOMe
Me
25-Acetoxy-20(S),24(R)-epoxydammaran-3~-ol
C32Hs404 (502.75)
22 23
Plates (MeOH), mp 188-190C, [am + 97.3
(CHC13, c 1.32)
IR (KBr): 998,1028,1112,1122,1218,1250,1372,
1460, 1696, 1710, 2950 cm-l
lH-NMR (60MHz,CDC13): 0.88, 0.93, 1.01, 1.06,
HO 1.18, 1.24 (18H,6xs,6x-Me), 1.44 (6H,bs,Me-
26,Me-27), 2.06 (3H,s,-OCOMe)
Me
28 MS, m/z 500 (M+,l %),485 (49),467 (3),425 (27),
398 (40), 356 (25), 315 (10), 313 (17),300 (21),
Needles (MeOH), mp 178-180C, [a]g + 55.0 273 (10),245 (100), 205 (90),185 (100), 125 (62)
(CHC13, c 1.424) ORD (MeOH) [P] (nm): + 1270 (400), + 4445
IR (KBr): 890, 930, 968, 1000, 1030, 1075, 1126, (306), + 710 (272), + 6190 (220)
1240, 1260, 1376, 1450, 1700, 2950, 3550 cm- 1 Deriv: 3-0xo-20(S),24(R)-epoxydammaran-25-
lH-NMR (60MHz,CDC13): 0.85, 0.89, 0.93, 0.98, 01, needles (MeOH), mp 152-154 DC, by saponifi-
1.08, 1.18 (18H,6xs,6x-Me), 1.25, 1.38 (2x3H, cation of 25-acetoxy-20(S),24(R)-epoxydam-
2xs,Me-26,Me-27), 2.06 (3H,s,-O-CO-Me) maran-3-one with KOH-MeOH
MS, m/z 502 (M+,l %),487 (35),442 (4),398 (4), StL: Pyxine coccifera (Fee) Nyl.
383 (12),358 (7),251 (14),248 (20),247 (18), 245 Lit: Huneck 1976
(10),207 (44), 185 (100)
ORD (MeOH) [P] (nm): + 582 (400), + 1420
(300), + 3052 (230) 3~-Acetoxyfern-9(I 1)-en-12~-ol
Deriv: 20(S),24(R)-Epoxy-dammaran-3~,25- C32Hs203 (484.74)
diol, needles (CHC13-MeOH), mp 198-199C,
[an4 + 27.5 (CHC13, c 1.44), by saponification of
25-acetoxy-20(S),24(R)-epoxydammaran-3~-01
with KOH-MeOH
StL: Pyxine coccifera (Fee) Nyl.
Lit: Huneck 1976
MeCOO
25-Acetoxy-20(S),24(R)-epoxydammaran-3-
one [25-Acetoxy-20(S),24(R)-epoxydammaran-
3-on]
C32Hs204 (500.47)
lH-NMR (300MHz,CDC1 3 ): 0.79, 0.80, 0.84
(3x3H,3xs,3x-Me), 0.84, 0.90 (2x3H,2xd,J=
6.5Hz,Me-29,Me-30), 0.94 (3H,s,-Me), 0.95
(3H,s,-Me) 1.13 (3H,s,-Me), 2.05 (3H,s,-
3.20 Terpenoids 363
OCOMe), 3.48 (lH,bd,J=5Hz,H-12), 4.47 (lH, C-23: 27.4, C-24; 16.2, C-25: 25.3, C-26: 15.7,
dd,Jl=6.6,J2=9.3Hz,H-3), 5.51 (lH,dd,Jl=2.1,J2= C-27: 17.1, C-28: 15.4, C-29: 22.0, C-30: 23.0,
5.0Hz,H-ll) C-3-0COMe: 21.4, C-3-0COMe: 171.2
13C-NMR (75.43MHz,CDCI3): C-l: 39.0, C-2: MS, m/z 484 (M+,30%), 469 (29), 451 (32), 409
24.6, C-3: 80.8, C-4: 38.3, C-5: 44.3, C-6: 18.9, (37), 391 (26),255 (29),43 (100)
C-7: 17.9, C-8: 40.3, C-9: 153.6, C-lO: 40.9, C- StL: Pseudocyphellaria aurata (Ach.) Vain.
11: 118.5, C-12: 173.1, C-13: 37.1, C-14: 37.8, C- TLC: A: 66, B': 60, C: 56, E: 48, G: 80
15: 28.3, C-16: 36.1, C-17: 43.3, C-18: 46.8, Lit: Wilkins and Elix 1990
C-19: 20.6, C-20: 31.3, C-21: 59.6, C-22: 30.4,
C-23: 27.4, C-24; 16.4, C-25: 24.6, C-26: 17.7,
12 a,-Acetoxyfern-9(11 )-en-3~-ol
C-27: 16.1, C-28: 14.3, C-29: 22.2, C-30: 23.0,
C-3-0COMe: 21.3, C-3-0~OMe: 170.9 C32H5203 (484.74)
MS, m/z 484 (M+,82%), 466 (6),451 (5),273 (28),
271 (50),255 (13), 135 (64),43 (100)
StL: Pseudocyphellaria aurata (Ach.) Vain.
TLC: A: 69, B': 65, C: 41, E: 53, G: 89
Lit: Wilkins and Elix 1990
3~-Acetoxyfern-9(11)-en-19~-ol
C32Hs203 (484.74) Crystals (MeOH), mp 268-270C, [a,]D + 86

(CHCI3, c 0.22)
IR (KBr): 920, 960, 970, 1020, 1195, 1260, 1380,
1450, 1730,2930, 3560cm- 1
IH-NMR (60MHz,CDCI3 ): 0.76, 0.87, 0.97, 1.07
(18H,4xs,6x-Me), 0.83, 0.89 (2x3H,2xd,Me-29,
Me-30), 1.98 (3H,s,-OCOMe), 5.02 (12H,bs),
5.11 (lH,bs,H-ll)
MS, m/z 484 (M+,l1%), 442 (18), 424 (lOO), 391
(8),295 (18),274 (43),259 (54), 255 (42)
Crystals, mp 200-202C Deriv: Fern-9(11)-ene-3~,12a,-diol) mp 208-
IH-NMR (300MHz,CDC13 ): 0.76, 0.80, (2x3H, 209C (MeOH), by saponification of 12 a,-
2xs,2x-Me), 0.83 (3H,d,J=6.5Hz,Me-29), 0.84 acetoxyfern-9(11)-en-3~-ol with KOH-MeOH
(3H,s,-Me), 0.88 (3H,d,J=6.5Hz,Me-30), 0.93, under reflux in 30 min
0.94, 1.09 (3x3H,3xs,3x-Me), 2.05 (3H,s,- StL: Xanthoria resendei Poelt et C.N.Tav.
OCOMe), 4.23 (IH,ddd,Jl=3.3,J2=J3=9.5Hz,H- TLC: A: 55, C: 45, E: 27, G: 60
19),4.48 (lH,dd,Jl=6.5,J 2=9.5Hz,H-3), 5.30 (lH, Lit: Gonzalez et al. 1974
m,H-ll)
13C-NMR (75.43MHz,CDCI3): C-l: 39.0, C-2:
24.7, C-3: 81.1, C-4: 38.2, C-5: 44.5, C-6: 19.0,
C-7: 17.9, C-8: 39.8, C-9: 150.5, C-lO: 37.1, C-
11: 116.3, C-12: 37.5, C-13: 37.6, C-14: 37.6, C-
15: 28.3, C-16: 36.3, C-17: 44.5, C-18: 57.3,
C-19: 71.3, C-20: 40.9, C-21: 59.2, C-22: 30.8,
3~- Acetoxyfern-9( 11 )-en-12-one 19 20

[3~-Acetoxyfern-9(11)-en-12-onl
C32H5003 (482.69)
MeCOa
Plates (CHClrMeOH), mp 273-275C

IR (KBr): 834, 864, 892, 906, 916, 940, 962, 978,
Me 1026, 1050, 1090, 1110, 1142, 1260, 1320, 1380,
Crystals, mp 266-268C 1412, 1450, 1466, 1702,2990,3500, 3620cm-1
IH-NMR (300MHz,CDCU: 0.78, 0.82, (2x3H, MS, mlz 502 (M+,12%), 484 (32), 466 (7), 441
2xs,2x-Me), 0.84, (3H,d,J=6.5Hz,Me-29), 0.87 (16),424 (20), 406 (15),384 (17), 366 (43),355
(3H,s,-Me), 0.89 (3H,d,J=6.5Hz,Me-30) 0.97, (12),351 (1I), 305 (12), 233 (10),229 (17),217
1.14, 1.19 (3x3H,3xs,3x-Me), 2.06 (3H,s,- (32),207 (73),203 (49), 189 (100), 175 (56), 161
OCOMe), 4047 (1H,dd,L=6.3, J2=9.3Hz,H-3), (58),149 (98), 135 (58), 121 (50),109 (44)
5.63 (IH,d,J=2.7Hz,H-l I) Deriv: 1~,3~-Diacetoxyhopan-22-ol, mp 256-
13C-NMR (75A3MHz,CDClJ: C-l: 37.8, C-2: 258C (CHC13-MeOH), [am + 37.4 (CHC13)
2404, C-3: 8004, C-4: 3804, C-5: 44.0, C-6: 18.5, IH-NMR (200MHz,CDC1 3 ): 0.71 (3H,s,Me-28),
C-7: 17.6, C-8: 41.9, C-9: 170.8, C-I0: 38.8, C- 0.81 (6H,s,Me-23,Me-24), 0.90 (3H,s,Me-25),
11: 121.0, C-12: 206.3, C-13: 51.4, C-14: 43.5, C- 0.93 (3H,s,Me-27), 0.98 (3H,s,Me-26), 1.15 (3H,
IS: 28.9, C-16: 35.3, C-17: 43.1, C-18: 46.6, s,Me-29), 1.17 (3H,s,Me-30), 1.66 (IH,m,H-2~)
C-19: 22.1, C-20: 2804, C-21: 58.6, C-22: 30.8, 1.87 (1H,m,H-2a), 1.95 (3H,s,I~-OAc), 1.99
C-23: 2704, C-24; 16.2, C-25: 23.6, C-26: 16.0, (3H,s,3~-OAc), 4.57 (1H,dd,H-3a), 4.65 (1H,
C-27: 14.9, C-28: 14.7, C-29: 22.3, C-30: 23.0, dd,H-la)
C-3-0COMe: 21.3, C-3-0COMe: 170.9 13C-NMR (50.33MHz,CDC13): C-l: 80.3, C-2:
MS, m/z 482 (M+,37%), 467 (52), 397 (44), 271 30.0, C-4: 37.8, C-5: 52.8, C-6: 17.7, C-7: 32.9,
(28), 135 (67),43 (100) C-8: 42.3, C-9: 50.7, C-I0: 42.2, C-ll: 23.0, C-
StL: Pseudocyphellaria aurata (Ach.) Vain. 12: 24.0, C-13: 49.3, C-14: 41.9, C-15: 34.5; C-
TLC: A: 72, B': 64, C: 56, E: 66, G: 39 16: 21.9, C-17: 53.9, C-18: 43.9, C-19: 41.2,
Lit: Wilkins and Elix 1990 C-20: 26.6, C-21: 51.1, C-22: 73.9, C-23: 27.8,
C-24: 16.9, C-25: 12.8, C-26: 16.0, C-27: 16.9,
C-28: 16.1, C-29: 28.7, C-30: 30.9, C-I-0-
3 ~- Acetoxyhopan -1 ~,22-diol COMe: C-3-0-COMe: 21.0, 21.7, C-I-0-
C32Hs404 (502040) COMe, C-3-0-.GOMe: 170.0, 170.2
StL: Canoparmelia texana (Tuck.) Elix et Hale
TLC: A: 51, B': 34, C: 39, E: 23, G: 53
Lit: 'Huneck et al. 1983
3.20 Terpenoids 365
6a-Acetoxyhopan-7 a,22-diol 13: 48.5, C-14: 44.1, C-15: 43.5, C-16: 66.8, C-
17: 60.7, C-18: 45.7, C-19: 41.6, C-20: 27.8, C-
C32Hs404 (502.75)
21: 50.8, C-22: 74.4, C-23: 36.3, C-24: 22.1,
C-25: 17.1\ C-26: 18.4, C-27: 17.0a, C-28: 18.0,
C-29: 27.0, C-30: 31.2, C-6-0COMe: 170.3, C-
6-0COMe: 22.1; values marked with a may be
exchanged
MS, m/z 502 (M+,l%) 484 (13), 442 (40), 426
(20), 424 (21), 409 (13), 406 (16), 391 (13), 384
OCOMe (7), 366 (14), 223 (5), 205 (57), 189 (100), 187
(46), 169 (16), 147 (46)
Crystals (EtOH-H 20), mp 198.5-199C, [an + Deriv: 6a, 16~-Diacetoxyhopan-22-ol, mp
46.6 (CHC13, c 0.075) 232C, [a]D + 109 (CHCU, from 6a-
IR (Nujol): 1265,1710,3410, 3500 cm-l acetoxyhopan-16~,22-diol with Ac 20-pyridine
IH-NMR (100 MHz,CDC13): 0.77 (3H,s,Me-28), StL: Parmelia entotheiochroa Hue
0.86 (3H,s,Me-23), 0.94 (3H,s,Me-25), 1.02 (3H, TLC: A: 37, B': 34, C: 34, E: 6, G: 38
s,Me-24), 1.05 (3H,s,Me-26), 1.11 (3H,s,Me- Lit: Yosioka et al. 1966c; Elix et al. 1982b; Elix
27), 1.17, 1.21 (2x3H,2xs,Me-29,Me-30), 2.08 and Ernst-Russell 1993
(3H,s,-OCOMe), 3.66, 3.74 (2x1H,2xd,H-6,
H-7)
Deriv: 6a-Acetoxy-7-oxo-hopan-22-ol, mp 229- 7a-Acetoxyhopan-6a,22-diol
230C, by oxidation of 6a-acetoxyhopan-7a,22- C32H s40 4 (502.75)
diol with Jones' reagent
Lit: Corbett and Cumming 1971
6a- Acetoxyhopan-16~,22-diol
C32Hs404 (502.40)
OH
Crystals (EtOH-H 2 0), mp 198-198.5C, [a]D +
22.2 (CHC13, c 0.14)
IR (Nujol): 1265, 1695, 3500 3560 cm- 1
IH-NMR (lOOMHz,CDClJ: 0.76 (3H,s,Me-28),
0.90 (3H,s,Me-25), 1.00 (3H,s,Me-24), 1.01
(3H,s,Me-26), 1.15 (6H,s,Me-23,Me-24), 1.16,
1.20 (2x3H,2xs,Me-29, Me-30) 2.05 (3H,s,-
Crystals, mp 225C, [a]D + 36 (CHC13) OCOMe), 3.70 (lH,q,H-6)
IR (CHC13): 1250, 1720, 3400cm-1 Deriv: 6-0xo-7a-acetoxyhopan-22-ol, mp 256-
IH-NMR (60MHz,CDC13): 2.05 (3H,s,-OCOMe), 257C, from 7a-acetoxyhopan-6a,22-diol with
5.20 (1H,bs,H-6), 4.10 (lH,bs,H-16) Jone's reagent
13C-NMR: C-1: 40.2, C-2: 18.4, C-3: 43.8, C-4: StL: Pseudocyphellaria crocata (1.) Vain.
33.2, C-5: 58.4, C-6: 71.8, C-7: 40.9, C-8: 42.8, TLC: C: 31
C-9: 49.3, C-10: 39.5, C-l1: 20.9, C-12: 23.5, C- Lit: Corbett and Cumming 1971
16~- Acetoxyhopan-6a,22-diol Rhombic plates (benzene), mp 235-236C

IH-NMR: C-l: 40.3, C-2: 18.5, C-3: 43.8, C-4:
C32 H s4 0 4 (502.75)
33.7, C-5: 6l.0, C-6: 68.7, C-7: 44.7, C-8: 43.0,
19
C-9: 49.1", C-I0: 39.5, C-ll: 2l.2, C-12: 23.7, C-
29 13: 49.4', C-14: 4l.8, C-15: 33.7, C-16: 21.5, C-
?~7~Me 17: 53.0, C-18: 43.9, C-19: 47.7, C-20: 78.1,
16 I
"OH
C-21: 56.9, C-22: 72.8, C-23: 36.8, C-24: 2l.8,
o Me C-25: 17.l b , C-26: 18.9, C-27: 16.9 b, C-28: 17.4,
CO 30 C-29: 28.3, C-30: 30.8, C-20-0~OMe, C-20-
Me
OCOMe: 2l.2 (values marked with a and b may
be exchanged)
OH
MS, m/z 502 (M+,2%), 484 (13), 442 (2),426 (2),
424 (27), 409 (6),406 (IO), 391 (5),384 (15), 366
Prisms, mp 213-214C (IO), 207 (34), 189 (70), 205 (27), 187 (36), 147
13C-NMR: C-l: 40.4, C-2: 18.5, C-3: 43.7, C-4: (100)
33.6, C-5: 6l.1, C-6: 69.1, C-7: 45.5, C-8: 43.0, StL: Physcia aipolia (Ehrh. ex Humb.) FUrn.
C-9: 49.2 C-lO: 39.3, C-ll: 20.9, C-12: 23.5, C- TLC: B': 30, C: 36, E: 18
13: 48.7, C-14: 44.1, C-15: 41.1, C-16: 73.3, C- Lit: Elix et al. 1982b
17: 56.9, C-18: 46.7, C-19: 4l.5, C-20: 27.9,
C-21: 5l.9, C-22: 73.2, C-23: 36.7, C-24: 22.1,
C-25: 17.1", C-26: 18.3, C-27: 16.9', C-28: 18.1, 6a-Acetoxyhopan-22-01, Acetylzeorin,
C-29: 27.3, C-30: 30.3, C-16-0COMe: 170.9, C- Lesdainin
16-0COMe: 2l.6 (values marked with a may be
exchanged)
MS, m/z 502 (M+,1 %),484 (15),442 (28),426 (4),
424 (22),409 (I8), 406 (4), 391 (9) 384 (100), 366
(26),207 (73), 189 (81), 205 (22), 187 (81), 147
(98)
StL: Physcia aipolia (Ehrh. ex Humb.) FUrn.
StL; A: 41, C: 32, E: 8, G: 36
20a-Acetoxyhopan-6a,22-diol Needles (acetone), mp 221-226C, [an + 78.1

(CHCI3, c 0.64)
C32Hs404 (502.75) lH-NMR (300MHz,CDCI3): 0.76 (3H,s,Me-28),
0.85 (3H,s,Me-24), 0.88 (IH,H-1a), 0.92 (4H,
2Q.. OCOMe H-19a,Me-25), 0.97 (3H,s,Me-27), 1.03 (3H,s,
Me-23), l.09 (3H,s,Me-26), 1.13 (IH,H-5a),
1.17 (3H,s,Me-29 or Me-30), 1.18 (2H,H-3a,H-
15a), l.20 (3H,s,Me-29 or Me-3~), l.28 (2H,H-
3~,H-13~), l.29 (IH,H-lla), l.35 (lH,H-9a),
l.36 (IH,H-15~), l.38 (lH,H-2a), 1.40 (2H,H-
12a,H-12~), l.43 (lH,H-17~), 1.47 (3H,H-7a,
OH H-7~,H-20~), l.50 (IH,H-19a), l.55 (2H,H-
3.20 Terpenoids 367
2-j3,H-ll~), 1.58 (lH,H-16a), 1.66 (1H,H-1~), fication of 7~-acetoxyhopan-22-o1 with KOH-

1.73 (1H,H-20a), 1.93 (lH,H-16~), 2.03 (3H,s, MeOH
-O-CO-Me), 2.24 (1H,H-21~) StL: Pseudocyphellaria billardieri (Del.) Ras.
J3C-NMR (75MHz,CDCI3 ): C-1: 40.2, C-2: 18.4, TLC: A: 63, B': 52, C: 46, E: 41, G: 61
C-3: 43.5, C-4: 33.2, C-5: 58.5, C-6: 72.0, C-7: MC: Figs. 54D; 55A
41.0, C-8: 42.8, C-9: 49.4, C-10: 39.6, C-ll: 21.1, Lit: Corbett and Young 1966a; Howarth et al.
C-12: 24.0, C-13: 49.9, C-14: 42.1, C-15: 34.3, 1983
C-16: 21.9, C-17: 54.0, C-18: 44.0, C-19: 41.3,
C-20: 26.6, C-21: 51.1, C-22: 73.8, C-23: 36.3,
15a-Acetoxyhopan-22-01, Dolichorrhizin
C-24: 22.2, C-25: 17.1, C-26: 18.1, C-27: 17.1,
C-28: 16.1, C-29: 28.9, C-30: 31.0, C-6-0-CO- C32 H s4 0 3 (486.75)
Me: 22.0, C-6-0-.GO-Me: 170.3
MS, m/z 486 (M+,2%), 471 (1),468 (2),428 (2),
426 (6),411 (2),408 (5),393 (2), 368 (5),352 (2),
289 (1), 229 (7), 207 (25), 189 (100), 149 (52)
Deriv: Zeorin, mp 236-242C, [an + 63.3
(CHCI3, c 0.56), by saponification of 6a-
acetoxyhopan-22-o1 with KOH-MeOH
StL: Physcia aipolia (Ehrh. ex Humb.) Fum.
Crystals (n-hexane), mp 200-201, 203-205C
TLC: A: 62, B': 56, C: 53, E: 40, G: 66
(acetone-MeOH), [a]o + 22.1 (CHCI3, c 0.58)
Lit: Wilkins et al. 1989a; Kummerling and
IH-NMR (60MHz,CDCI 3 ): 0.82, 0.86, 1.06, 1.11,
Leuckert 1993, Leuckert et al. 1995
1.16, 1.20 (24H,6xs,8x-Me), 1.93 (3H,s,-
OCOMe), 5.03 (1H,m,H-15)
7~- Acetoxyhopan-22-01 MS, m/z 468 (10%),427 (4),409 (2), 368 (4),247
(3), 222 (8), 206 (20), 204 (21), 191 (100), 188
C32 H s40 3 (486.75) (20), 164 (16), 148 (22),43 (94)
Deriv: Hopan-15a,22-diol, mp 249C (benzene),
[a]o + 34 (CHCI3, c 1.3), from 15a-aceto-
xyhopan-22-o1 by saponification with KOH-
MeOH
TLC: A: 61, C: 44, G: 58
Lit: Takahashi et al. 1969; Renner et al. 1982
Crystals (benzene), mp 247-248C, [an + 26
(CHCI3, c 0.71)
IR (KBr): 785, 838, 860, 892, 926, 950, 965, 990, 16~- Acetoxyhopan-22-01
1020, 1035, 1095, 1120, 1142, 1164, 1205, 1270,
C32 H s40 3 (486.75)
1370,1390,1470, 1700,3000, 3630cm-1
IH-NMR (60 MHz,CDCI3 ): 0.78, 0.83, 1.03, 1.10,
1.17 (24H,5xs,8x - Me), 1. 97 (3 H,s, -OCO Me),
5.10 (lH,q,H-7)
MS, m/z 468, 453, 426, 189
Deriv: Hopan-7~,22-diol, mp 229C (EtOH,
sintering between 180 and 200C), by saponi-
Crystals, mp 228C, [a]D + 52 (CHCI3 ) 30

Me
IR (CHCI3): 1200-1240, 1735, 3550cm-1
lH-NMR (60MHz,CDCI3 ): 2.10 (3H,s,-OCOMe),
4.75 (lH,m,H-16)
Deriv: Hopan-16~,22-diol, mp 268C, [a]D +
68 (CHCI3 ), by saponification of 16~-aceto
xyhopan-22-o1 with KOH-MeOH
StL: Parmelia entotheiochroa Hue
Lit: Yosioka et al. 1966c
Crystals, mp 114-116C (after sublimation)
IR (Nujol): 888, 1635, 1245, 1735, 3450cm-1
lSa-Acetoxy-22-hydroxyhopan -24-oic acid, lH-NMR (CDCI3 ): 0.73 (3H,s,Me-28), 0.84 (3H,
Amphistictinic acid {l5a-Acetoxy-22- s,Me-29), 0.87 (3H,s,Me-27), 0.98 (3H,s,Me-
hydroxyhopan-24-saure, Amphistictinsaure) 30), 1.03 (6H,s,Me-25,Me-26), 1.78 (3H,s,Me-
24) 2.03 (3H,s,-OCOMe), 3.15 (lH,s,H-22), 3.98
C32Hs20S (516.77)
(2H,bs,-CH 2-3), 4.82 (2H,bs,=CH z-23)
Deriv: 3,4-Secostict-4(23)-en-3,22a-diol, mp
. 2f::~~ 88-90C (after sublimation), by saponification
of 3-acetoxy-3,4-secostict-4(23)-en-22-o1 with
Me KOH-MeOH
StL: Pseudocyphellaria degelii D.Gall.
Lit: Goh et al. 1979
24
Crystals (Et 20), mp ISO-152C (softening above

2a- Acetoxystictan -3~,22a-diol
120C)
IR (KBr): 1242-1254, 1694, 1734, 2800- C32 H s4 0 4 (502.75)
3600cm-1
lH-NMR (CDCI 3): 0.74 (3H,s,Me-25), 0.79 Me
(3H,s,Me-28), 1.06 (3H,s,Me-26), 1.09 (3H,s,
Me-27), 1.13, 1.18 (2x3H,2xs,Me-29,Me-30),
1.21 (3H,s,Me-23), 1.95 (3H,s,-OCOMe) MeOCO.,2
Deriv: Methyl 15a-acetoxy-22-hydroxyhopan-
24-oate, mp 69-71C (Et20-n-hexane), from
15a-acetoxy-22-hydroxyhopan-24-oic acid with
CH2N2 in Etp at 20C in 4h Crystals (EtOH), mp 215-216C, [anD - 42.0
StL: Pseudocyphellaria a.mphisticta (Kn.) D.Gall. (CHCI 3, c 0.36)
et P. James IR (Nujol): 1250, 1730,3440, 3580cm-1
Lit: Ronaldson and Wilkins 1978 lH-NMR (100MHz,CDCI3 ): 0.73, 0.86, 0.91, 0.98,
0.99, 1.04, 1.14 (24H,7xs,8x-Me), 2.05 (3H,s,-
3-Acetoxy-3,4-secostict-4( 23 )-en-22a-ol OCpMe), 3.14, 3.18 (2x1H,2xd,H-3,H-22), 5.01
{lH, sextet, H-2)
C32H s4 0 3 (486.75) Deriv: 2a,3 ~,22a- Triacetoxystictane, mp 274C
(acetone), from 2a-acetoxystictan-3~,22a-diol
with AczO-pyridine at 20C in 48h
3.20 Terpenoids 369
S1L: Pseudocyphellaria flavicans (Hook. et Tayl.) IR (Nujol): 1245, 1730, 3420 CIlll
Vain. lH-NMR (l00MHz,CDCl3): 0.74 (3H,s,Me-28),
TLC: A: 45, B': 33, C: 37, E: 19, G: 44 0.86 (9H,s,Me-23,Me-24,Me-29), 0.89 (3H,s,
Lit: Chin et al. 1973 Me-25), 0.93 (3H,s,Me-27), 0.98 (3H,s,Me-30),
1.14 (3H,s,Me-26), 2.04 (3H,s,-OCOMe), 3.14
(lH,d,H-22), 4.51 (lH,m,H-3)
3~- Acetoxystictan -2a,22a-diol
Deriv: Stictan-3~,22a-diol, mp 283 DC (CHCl3-
C32Hs404 (502.75) acetone), [anD + 12.3 (CHC13, c 1.10), by sapo-
nification of 3~-acetoxystictan-22a-ol with
Me KOH-MeOH
StL: Pseudocyphellaria flavicans (Hook. et Tayl.)
Vain.
Lit: Chin et al. 1973
Acetyl-iso-arborinol
Crystals (after sublimation), mp 227 DC, [anD- C32 H s2 0 Z (468.74)
58.2 (CHCl3, c 0.62)
IR (Nujol): 1250, 1735,3440, 3450cm- l
lH-NMR (100MHz,CDCl3): 0.73, 0.87, 0.91, Me
0.96, 0.98, 1.16 (24H, 6xs,8x-Me), 2.12 (3H,s,-
OCOMe), 3.14 (lH,d,H-22), 3.83 (lH,sextet,H-
2),4.50 (lH,d,H-3)
Deriv: 2a,3~,22a- Triacetoxystictane, mp 274 DC
(acetone), from 3~-acetoxystictan-2a,22a-diol
with Ac 20-pyridine at 20 DC in 48 h
StL: Pseudocyphellaria flavicans (Hook. et Tayl.) Crystals (MeOH-EtOAc), mp 285 DC, [am + 48.0
Vain. (CHCl3, c 0.26)
TLC:C:40,E:57,G:49 IR (CHC13): 970, 1030, 1145, 1170, 1250,
Lit: Chin et al. 1973 1730cm-1
lH-NMR (200MHz,CDClJ: 0.50-1.10 (24H,8x-
Me), 2.05 (3H,s,-OCOMe), 4.49 (lH,dd,J=4.0,
3~- Acetoxystictan-22a-ol
10.0 Hz,H-3), 5.23 (lH,deformed d,H-ll)
C32Hs403 (486.75) StL: Cladonia macaronesica Ahti
Lit: Gonzalez et al. 1991
Me'
16-0-Acetylleucotylic acid
(16-0-Acetylleucotylsaure)
C32HszOs (516.74)
Crystals (after sublimation), mp 243-244 DC,

[anD - 12.2 (CHCl3, c 0.95)
Acetyltylolupenol B
. ..?;: ME' C32 H sz O z (468.74)
16 I "OH
o ME'
Ac
HOOC'"
23 ME'
Deriv: Methyl 16-0-acetylleucotylate, needles

(MeOH-HzO), mp 116, 176C (n-hexane), [a]D
+ 95 (CHCI3, c 0.95)
IR (Nujol): l240, 1730, 1755, 3555 cm- 1
lH-NMR (60MHz,CDCI3): 0.86 (6H,s,2x-Me),
0.98 (3H,s,-Me), 1.16 (12H,s,4x-Me), 2.06 (3H,
s,-O-CO-Me), 3.64 (3H,s,-COOMe) lH-NMR: 0.68, 0.76, 0.84, 0.92, 0.94, 1.09
StL: Parmelia entotheiochroa Hue (6x3H,6xs,6x-Me), 0.87, 0.90 (2x3H,2xd, J=6Hz,
TLC:C:39,E:2,G:36 Me-29,Me-30), 2.06 (3H,s,-OAc), 4.49 (1H,dd,
Lit: Yosioka et al. 1972a J=7.0, 9.5Hz,H-3), 5.35 (lH,m,H-11)
13C-NMR: 14.39, 15.99, 16.19, 21.33, 22.34,
3-0-Acetylpyxinol 23.36, 25.37, 27.42, 32.8 (9xMe-), 18.23, 19.09,
24.67,27.60,28.97,32.28,37.61,38.31,38.91 (9x-
C3zHs40S (518.75) CH z-), 35.88, 40.89, 44.42, 49.44, 53,98, 81.03,
116.20 (7x=CH-), 36.74, 36.97, 38.11, 41.34 (2),
. . r<~: 26 149.91 (6x=C=), 171.02 (-CO-)

MS, mlz: 468 (M+,36%), 453 (31),441 (20),423
Me (28),410 (47),409 (100),393 (22), 367 (8), 313
3 27
(5), 301 (14), 287 (24), 273 (21), 271 (11), 257
MeOCO .'
Me" Me (14), 241 (14), 229 (9), 219 (11), 207 (15), 205
29 28
(15), 204 (12), 191 (20), 189 (18), 175 (9), 149
Crystals (MeOH-HzO), mp 196-197C, [a]D + (11), 135 (17), 123 (17), 121 (21),109 (28), 107
28.2 (CHCI3, c 1.06) (22)
IR (CCI 4): 1245, 1730, 3450cm- 1 Deriv: Tylolupenol B, mp 177-178C, [a]D":" 6.1
lH-NMR (60MHz,CDCIJ: 0.85 (6H,s,Me-28, (CHC13), by saponification of acetyltylolupenol
Me-29), 0.89 (6H,s,Me-19, Me-30), 0.99 (3H, B with KOH-MeOH
s,Me-18), 1.10 (3H,s,Me-21), 1.28 (6H,s,Me-26, StL: Usnea articulata (1.) Hoffm.
Me-27), 2.03 (3H,s,-OCOMe), 3.53 (lH,sextet, Lit: Kawanishi et al. 1985; Ali 1992
H-12), 3.86 (1H,t,H-24), 4.51 (1H,t,H-3)
MS, mlz 503 (3%),500 (3),485 (3),482 (3),459
Aipolic acid (Aipolsaure)
(4),249 (7), 189 (25), 143 (100)
Deriv: Triacetylpyxinol, needles (MeOH-HzO), C3zHs20S (516.74)
mp 180-181C, from 3-0-acetylpyxinol with
ACzO-NaOAc by heating under reflux for 2h
StL: Pyxine endochrysina Nyl.
3.20 Terpenoids 371
Me
OCOMe
The physical data of the free acid are unknown Needles (CH 2 C1 2-MeOH), mp 183-187C, [al D +
Deriv: Methyl aipolate, gum, from aipolic acid 82 (CHC1 3 )
with CH 2N2 MS, m/z 426 (M+), 218, 203, 189, 175, 161, 135,
lH-NMR (300MHz,CDC13): 0.75 (3H,s,Me-28), 95, 69
0.84 (3H,s,Me-24), 0.91 (1H,H-1a), 0.93 (3H, Deriv: Acetyl-a-amyrin, mp 220-227C, [al D +
s,Me-26), 0.96 (3H,s,Me-27), 1.07 (3H,s,Me- 83 (CHCU, from a-amyrin with Ac 2 0-pyridine
23), 1.17 (3H,s,Me-29 or Me-30), 1.20 (3H,s, StL: Flavocetraria nivalis (1.) Karnef. et Thell
Me-29 or Me-30), 1.36 (1H,H-5a), 1.48 (lH,H- Lit: Bruun 1969
7a), 1.62 (1H,H-7~), 2.04 (3H,s,-O-COMe),
2.22 (lH,H-21~), 2.62 (1H,H-1~)
13C-NMR (75MHz,CDC13 ): C-1: 38.4, C-2: 19.4, ~-Amyrin
C-3: 42.5, C-4; 33.7, C-5: 57.9, C-6: 71.5, C-7: C30HSOO (426.70)
40.2, C-8: 42.2, C-9: 49.2, C-10: 51.2, C-ll: 21.9,
C-12: 24.1, C-13: 49.9, C-14; 42.2, C-15: 34.8, Me
C-16: 21.9, C-17: 53.9, C-18: 44.0, C-19: 41.3,
C-20: 26.6, C-21: 50.9, C-22: 73.6, C-23: 35.7,
C-24; 23.5, C-25: 175.5, C-26: 15.7, C-27: 16.7,
C-28: 16.3, C-29: 28.8, C-30: 31.0, C-6-0-CO-
Me: 22.2, C-6-0-CO-Me: 170.0, -COOMe: 51.0
MS, m/z 512 (0.5%),470 (5),412 (9),411 (18),
393 (7),353 (5),219 (31), 191 (30),189 (91), 149
(33), 119 (52), 95 (72),59 (100)
StL: Physcia aipolia (Ehrh. ex Humb.) Fum. Crystals, mp 194-200C, [am + 87 (CHC1 3 )
from Kenya MS, m/z 426 (M+), 218, 203, 189, 175, 161, 135,
Lit: Wilkins et al. 1989a 95,69
Deriv: Acetyl-~-amyrin, mp 237-242C, [anD +
a-Amyrin 80 (CHC1 3 ), from ~-amyrin with Ac2 0-pyridine
C30HSOO (426.70) Lit: Allemand 1988
a-Amyrone, a-Amyrenone 6a, 16~- Diacetoxyhopan-22-ol

(a-Amyron, a-Amyrenon)
C34Hs60S (544.78)
C30H4S O (424.68)
Me
OCOMe
Crystals, mp 232C, [a]D + 109 (CHC13)

IR (Nujol): 1245, 1730, 3400 cm- 1
Crystals, mp 124-126C, [an + 109 (CHC13, c IH-NMR (60MHz,CDC13): 2.07, 2.10 (2x3H,2xs,
1.3) 2x-OCOMe), 5.20 (2H,2xbs,H-6,H-16)
IH-NMR (CDC13): 0.50-1.10 (24H,8x-Me), 5.15 13C-NMR: C-1: 40.2, C-2: 18.4, C-3: 43.4, C-4:
( 1H,t,J=3.5Hz,H-12) 33.2, C-5: 58.3, C-6: 71.8, C-7: 40.8, C-8: 42.8, C-
MS, m/z 424 (M+,21 %), 409 (12), 218 (100), 205 9: 49.2, C-10: 39.5, C-11: 20.8, C-12: 23.4, C-13:
(14),203 (28), 189 (18), 133 (16) 48.6, C-14: 44.1, C-15: 41.1, C-16: 73.3, C-17:
StL: Cladonia macaronesica Ahti 56.9, C-18: 46.7, C-19: 41.5, C-20: 27.8, C-21:
Lit: Gonzalez et al. 1991 51.8, C-22: 73.1, C-23: 36.3, C-24: 22.1, C-25:
17.1", C-26: 18.4, C-27: 16.9", C-28: 18.1, C-29:
27.4, C-30: 30.4, C-16-0.c;OMe: 170.1, C-6-
~-Amyrone, ~-Amyrenone
OCOMe: 22.1, C-16-0.c;OMe: 170.5, C-16-
(~-Amyron, ~-Amyrenon)
OCOMe: 21.7. Values marked with a may be
C30 H4sO (424.68) exchanged
MS, m/z 544 (M+,l %),526 (1), 484 (47),466 (35),
Me 451 (3),426 (36),424 (13),409 (11),406 (11), 391
(22), 366 (66),205 (19), 189 (IOO), 187 (70), 147
(56)
Deriv: Leucotylin, mp 335-336C, [an + 56.5
(CHC13, c 0.566), by saponification of 6a,16~
diacetoxyhopan-22-ol with KOH-MeOH
StL: Parmelia entotheiochroa Hue
TLC: A: 50, B': 37, C: 40, E: 4, G: 45
Me
Lit: Yosioka et aI. 1966c; Elix et al. 1982b
Crystals mp 178-180C, [a]ff + 109 (CHC13, c
1.5) 3~,22a- Diacetoxystictane
MS, mlz 424 (M+), 218, 203,189,175,109,55,41 (3 ~,22a- Diacetoxystictan)
StL: Evernia prunastri (L.) Ach.
Lit: Allemand 1988 C34Hs604 (528.79)
3.20 Terpenoids 373
30 Deriv: Stictan-2a,3~,22a-triol, mp 276C (ac-

Me
etone), [ali? + 15.2 by saponification of 2a,3~
diacetoxystictan-22a-ol with KOH-MeOH
Vain.
2a,3~- Diacetoxystictan-22-one
Crystals (acetone), mp 281-283C, [am - 14.7 (2a,3~-Diacetoxystictan-22-on)
(CHCI3, c 0.47)
C34Hs40S (542.77)
IR (Nujol): 1245, 1730cm-1
IH-NMR (100MHz,CDCI3 ): 0.81 (3H,s,Me-28), Me
0.85 (9H,s,Me-23,Me-24,Me-29), 0.89 (3H,s,
Me-25), 0.93 (6H,s,Me-27,Me-30), 2.03, 2.04
(2x3H,2xs,2x-OCOMe), 4.50(lH,m,H-3), 4.70
(lH,d,H-22)
Deriv: Stictan-3~,22a-diol, mp 283C (CHCI3-
acetone), [anD + 12.3 (CHCI3, c 1.1), by sapo-
nification of 3~,22a-diacetoxystictane with Crystals (acetone), mp 263-264C, [am - 32.8
KOH-MeOH (CHCI3, c 0.92)
StL: Pseudocyphellaria flavicans (Hook. et Tayl.) IR (Nujol): 1245, 1700, 1740cm-1
Vain. IH-NMR (l00MHz,CDCI3): 0.62, 0.90,1.01,1.03,
Lit: Chin et al. 1973 1.19 (24H,5xs,8x-Me), 1.97, 2.03 (2x3H,2xs,
2x-OCOMe), 4.73 (lH,d,H-3), 5.16 (lH,sextet,
2a,3~- Diacetoxystictan-22a-ol
H-2)
C34Hs60S (544.79) Vain.
Me
Diacetyl-12-deoxypyxinol
C34Hs60S (544.78)
26
_24 Me
-(OeOMe
Crystals (acetone), mp 231-232C, [anD - 1.5 Me
(CHCI3, c 1.00) 27
MeOeO 3
IR (Nujol): 1225, 1255, 1715, 1735, 3550 cm- l Me--
IH-NMR (100MHz,CDCI3): 0.72, 0.86, 0.90, 29
0.91,0.98, 1.04, 1.15 (24H,7xs,8x-Me), 1.97,2.03
(2x3H,2xs,2x-OCOMe), 3.14 (lH,d,H-22), 4.72 Needles (CHCI3-MeOH), mp 190-193C, [al D +
(lH,d,H-3), 5.16 (IH,sextet,H-2) 37.5 (CHCI3 , c 1.02)
IR (CCI4): 1245, 1735cm-1 6a,22-Dihydroxyhopan-23-oic acid

IH-NMR (60MHz,CDCIJ: 0.85 (l2H,s,Me-28, (6a,22-Dihydroxyhopan -23-saure)
Me-29,Me-19,Me-30), 0.94 (3H,s,Me-18), 1.09
(3H,s,Me-21), 1.42 (6H,s,Me-26,Me-27), 1.93, C30HS004 (474.70)
2.00 (2x3H,2xs,2x-OCOMe), 3.85 (lH,t,H-24),
4044 (lH,q,H-3) 23
..... ~COOH
MS, m/z 529 (l %),484 (41),383 (34),249 (4), 189
221 "OH
(47), 185 (89), 125 (l00)
Me
Deriv: 12-Deoxypyxinol, mp 197-198C
(MeOH-H 2 0), [a]D + 3004 (CHCI3, c 1.01), by
saponification of diacetyl-12-deoxypyxinol with
KOH-MeOH under reflux in 2h
StL: Pyxine endochrysina Nyl. Physical data unknown
Lit: Yosioka et al. 1972c MS, m/z 226,210,208
StL: Pseudocyphellaria Javeolata (DeL) Malme
Diacetylpyxinol TLC: A: 18, B': 31, C: 14, E: 7
Lit: Wilkins and James 1979
C34Hs606 (560.79)
Fern-9(11)-en-3p,12a-diol
26
'. ~Me C30HSOOZ (442.70)
"', "'OCOMe
Me
27
MeOCO 3
Me Me
29 28
Needles (EtOAc), mp 240-241C, [a]D + 10

(CHCI 3, C 1.00)
IR (Nujol): 1020, 1235, 1245, 1730, 3420 cm-I; Crystals (MeOH), mp 208-209C [a]D 0
KBr: 766, 892, 902, 930, 946, 996, 1030, 1076, (CHCI3, c 0.25)
1104, 1156, 1240, 1304, 1364, 1460, 1620, l720, IR (CHCI3): 920,1010,1380,1470,3440, 3600 cm-l
2980, 3480 cm- 1 lH-NMR (60MHz,CDCI3 ): 0.77, 0.82, 0.88, 0.97,
lH-NMR (100MHz,CDCI3): 0.84 (6H,s,Me-28, 1.08 (18H,5xs,6x-Me), 0.83, 0.89 (2x3H,2xd,
Me-,-29), 0.87 (3H,s,Me-.19), 0.91 (3H,s,Me-30), J=7Hz,Me-29,Me-30), 3.30 (lH,t,J=8Hz,H-3),
0.99 (3H,s,Me-18), 1.24 (3H,s,Me-21), lAS, 3.90 (lH,bs,H-12), 5.20 (lH,bs)
1.52 (2x3H,2xs,Me-26,Me-27), 2.06 (6H,s,2x- MS, m/z 442 (M+,100%), 424 (12), 409 (8), 273
OCOMe), 3047 (lH,sextet,H-12), 4.11 (lH, (48),271 (54),255 (22)
t,J=6AHz,H-24), 4.52 (lH,bs,HO-12) Deriv: 3p,12a-Diacetoxyfern-9(l1)-en, mp 186-
Deriv: Pyxinol, needles (MeOH-H 2 0), mp 225- 188.o C (MeOH), [a]D + 99 (CHCI3, c 0.24), from
226C, [a]D + 62.8 (CHCI3, c 0.99), by saponifica- Fern-9(l1)-en-3p,12a-diol with ACzO-pyridine
tion of diacetylpyxinol with KOH-MeOH StL: Xanthoria resendei Poelt et Tav.
StL: Pyxine endochrysina Nyl. TLC: A: 40, B': 36, C: 35, E: 7, G: 91
Lit: Yosioka et aL 1969c, 1972c Lit: Gonzalez et aL 1974
3.20 Terpenoids 375
Fern-9(ll)-en-3~,12~-diol Crystals (MeOH), mp 250-251C, [al D - 45

(CHC13, c 2.16)
C30HSOOZ (442.70)
UV (MeOH): 246nm (4.00)
IR (KBr): 870, 1120, 1612, 1680, 1715cm-1
IH-NMR (60 MHz,CDC13): 0.79, 0.86, 1.08, 1.17,
1.20, 1.38 (6x3H,bxs,6x-Me), 0.85, 0.92 (2x3H,
2xd,J=7Hz,Me-29,Me-30), 5.75 (lH,d,J=3Hz,
H-ll)
HO MS, m/z 438 (M+,100%), 423 (58),395 (56),287
Me" (5),273 (20),271 (34),255 (3)
23 Deriv: Fern-9(11)-en, mp 173C (MeOH), [al D -
18 (CHC1 3, c 1.25), from fern-9(11)-en-3,12-
Crystals, mp 210-212 c dione by W olff-Kishner reduction
IH-NMR (300MHz,CDC13): 0.78, 0.80 (2x3H, StL: Xanthoria resendei Poelt et Tav.
2xs,2x-Me), 0.84 (3H,d,J=6.5Hz,H-29), 0.88 TLC: A: 55, B': 48, C: 53, E: 48, G: 78
(3H,s,-Me), 0.90 (3H,d,J=6.5Hz,Me-30), 0.94, Lit: Gonzalez et al. 1974
0.96,1.10 (3x3H,3xs,3x-Me), 3.19 (lH,dd,L=6.3,
Jz=9.5 Hz,H-3), 3.45 (lH,bd,J=5.6Hz,H-12), 5.51
Friedelan-3~-ol, Epifriedelinol
(lH,dd,JI=2.4,Jz=5.4Hz,H-l1)
13C-NMR (75.43MHz,CDC13): C-1: 39.2, C-2: C30H s2 0 (428.72)
28.1, C-3: 79.0, C-4: 39.4, C-5: 44.0, C-6: 19.1,
C-7: 18.0, C-8: 40.3, C-9: 153.6, C-10: 41.0, C-
11: 118.2, C-12: 73.1, C-13: 37.1, C-14: 37.8, C-
IS: 28.3, C-16: 36.0, C-17: 43.4, C-18: 46.8,
C-19: 20.6, C-20: 31.1, C-21: 59.5, C-22: 30.8,
C-23: 27.5, C-24: 15.1, C-25: 24.6, C-26: 17.8,
HO
C-27: 16.5, C-28: 14.3, C-29: 22.2, C-30: 21.1
MS, m/z 442 (M+,23%), 424 (7), 409 (7),273 (18),
271 (29),255 (l6), 135 (61),43 (l00) Crystals (CHzClz-MeOH), mp 278-280C, [anD
StL: Pseudocyphellaria aurata (Ach.) Vain. + 21 (CHC13, c 1.0)
TLC: A: 45, B: 41, C: 40, E: 15, G: 50 IR (Nujol): 720,920,980,1000,1040,1050, 1180,.
Lit: Wilkins and Elix 1990 1390, 1480, 2860, 2950, 3490 cm- I
Deriv: Acetylfriedelan-3~-01, mp 282-293C,
Fern-9(ll )-en-3,12-dione [al5 + 38 (CHCI 3, c 1.0), from friedelan-3~-01
[Fern-9{l1)-en-3,12-dionl with AczO-pyridine
StL: Flavocetraria nivalis (1.) Karnef. et Then
C30H460Z (438.67) Lit: Bruun 1954a, 1969; Bruun and Jefferies 1954
29
.. (Me Friedelin
Me
30

Lit: Corbett and Young 1966a; Corbett
and Cumming 1971; Corbett and Wilkins
1977
a
Hopan-1Sa,22-diol
Flat needles (CH 2CI2-MeOH), mp 261-263C, C30Hs202 (444.72)
[a]D + 25 (CHCI3)
IR (Nujol): 720, 1080, 1380, 1390, 1470, 1720,
2880, 2940 cm- 1
IH-NMR (100MHz,CDCI3): 0.73, 0.88, 0.92, 0.96,
1.01, 1.06 (8xMe)
MS, m/z 426 (M+,100%), 411 (27), 341 (9), 302
(41),273 (45),246 (12),232 (20), 218 (32),205 Crystals (benzene), mp 249C, [an + 34 (CHCI3,
(45), 179 (36), 163 (36), 125 (63), 123 (63), 95 c 1.30)
(91), 81 (36),69 (98), 55 (81) IR (KBr): 730, 845, 862,938,950,980, 1008, 1030,
Deriv: Friedelinoxime, mp 289-292 C, from 1050, 1116, 1150, 1162, 1202, 1225, 1380, 1464,
friedelin with hydroxylamine hydrochloride in 3000, 3500 cm- 1
pyridine IH-NMR (60MHz,CDCI 3): 0.78 (3H,s,Me-28),
StL: Evernia prunastri (1.) Ach., Flavocetraria 0.82, 0.85 (3x3H,2xs,Me-23,Me-24,Me-2S),
nivalis (1.) Karnef. et Thell 1.02 (3H,s,Me-27),1.08 (3H,s,Me-26)
MC:Fig.56A MS, m/z 444 (M+,48%), 426 (4),411 (4),386 (4),
Lit: C.F. Culberson 1969; Nicollier et al. 1979b 223 (8),205 (25), 191 (100), 165 (13)
Deriv: 15a-Acetoxyhopan-22-ol, mp 200-201C
Hopan-7p,22-diol (n-hexane), from hopan-15a,22-diol with Ac 20-
pyridine
C30 H sP2 (444.72) StL: Pseudocyphellaria billardieri (Del.) Ras.
TLC: A: 40, B': 39, C: 36, E: 12, G: 42
MC: Fig. 55B,C,D
Lit: Corbett and Young 1966b
Hopan-16p,22-diol
C30Hs202 (444.72)
Crystals (EtOH), mp 229C, [an + 23 (CHCI3)
IR (Nujol): 1034, 1044, 1165,3340 cm- 1
IH-NMR (60MHz,CDCI3): 0.80 (9H,s,Me-23,
Me-24,Me-28), 0.87 (3H,s,Me-25), 0.98 (3H,
s,Me-26), 1.05 (3H,s,Me-27)
MS, m/z 444 (M+), 207, 189 (100%)
Deriv: 7-0xohopan-22-ol, mp 256C, [an - 31
(CHCI3), from hopan-7p,22-diol with Cr0 3- Crystals, mp 268C, [a]D + 68 (CHC13)
pyridine IR (CHC13): 3350cm- 1
3.20 Terpenoids 377
Deriv: 16~-Acetoxyhopan-22-ol, mp 228C, [aJD . Plates (CHCI3-acetonitrile), mp 219-222 C, [aJD

+ 52 (CHCl3 ), from popan-16~,22-diol with + 86 (CHCl 3 , c 0.65)
ACzO-pyridine StL: not yet found in lichens
StL: Parmalia entotheiochroa Hue Lit: Starratt 1969
3~-Hydroxyhopan-29-oic acid
Hopan-6a,7a,22-triol (3~-Hydroxyhopan-29-saure)
C30Hsz03 (460.72) C30HS003 (458.70)
29
......(COOH
Me
Crystals (after sublimation), mp 230-231C, IR: 1360, 1470, 1720,2800,3000, 3400cm-1

[an + 36.2 (pyridine, c 0.24) lH-NMR: 0.76 (6H,s,Me-23,Me-28), 0.80 (3H,s,
IR (Nujol): 3350 cm- 1 Me-24), 0.95 (3H,s,Me-26) 0.96 (3H,s,Me-25)
lH-NMR (I00MHz,CDCl3): 0.77 (3H,s,Me-28), MS, m/z 458 (M+), 425, 397, 385, 221, 207, 177,
0.90 (3H,s,Me-25), 1.01 (3H,s,Me-24), 1.06 (6H, 147,107,95,81,55
s,Me-26,Me-27), 1.18 (3H,s,Me-29), 1.20 (6H,s, StL: Evernia prunastri (L.) Ach.
Me-23,Me-30) Lit: Allemand 1988
Deriv: 6a,7a-Diacetoxyhopan-22-ol, mp 222C
(EtOH-HzO), from hopan-6a,7a,22-triol with
3~- Hydroxy-30-nor-hop an-22-one
acetyl chloride and N,N-dimethylaniline in
(3~-Hydroxy-30-nor-hopan-22-on)
CHCl3 under reflux for 20 h
StL: Nephroma laevigatum Ach., Pseudo- CZ9H4S02 (428.67)
cyphellaria crocata (L.) Vain.
Hop-21~H-22(29)-en-3-one,Hopenone-B
[Hop-21~H-22(29)-en-3-on,'Hopenon-BJ
C30H4S04 (424.68)
Me
lH-NMR: 0.76 (3H,s,Me-23), 0.81 (3H,s,Me-24),

0.94 (3H,s,Me-27), 0.97 (6H,s,Me-25,Me-26),
2.16 (3H,s,Me-29)
MS, m/z 428 (M+), 273, 207, 191, 189, 135,95,69,
55,43
StL: Evernia prunastri (1.) Ach. lH-NMR (100MHz,CDCI3 ): 0.74 (3H,s,Me-28),

Lit: Allemand 1988 0.77 (3H,s,Me-25), 0.86 (3H,s,Me-29), 0.94 (3H,
s,Me-27), 1.00 (3H,s,Me-30), 1.04 (3H,s,Me-
24), 1.05 (3H,s,Me-23), 1.17 (3H,s,Me-26), 3.14
3~- Hydroxyolea-12-en-11-one
(lH,d,H-22)
(3~-Hydroxyolea-12-en-11-on)
MS, m/z 442 (M+,33%), 427 (15), 424 (54), 409
C30H4S0Z (440.58) (36), 381 (22), 342 (6), 222 (24), 207 (87), 205
(66), 189 (100), 175 (18), 163 (27), 151 (33), 139
Me.. Me
(28), 135 (52), 123 (51), 121 (51), 109 (72), 107
(48),95 (84), 81 (98),71 (45),67 (54), 57 (60),55
(98), 44 (95), 43 (99)
Deriv: Stictan-3,22-dione, mp 241-242 GC (ac-
etone), from 22a-hydroxy-stictan-3-one by oxi-
dation with Jones' reagent
Vain.
Lit: Chin et al. 1973; Wilkins 1977
Crystals, mp 212-231 GC, [a]n + 103 (CHCIJ
MS, m/z 438, 423, 299, 273, 232, 135, 95
Deriv: 3~-Acetoxyolea-12-en-ll-one, mp 259- 22a-Hydroxy-3,4-secostict-4(23 )-en-3-al
262 GC, [a]n + 109 (CHCI3 ) from 3~-hydro [22a-Hydroxy-3,4-secostict-4(23)-
xyolea-12-en-ll-one with Ac2 0-pyridine en-3-aldehyd]
C30HsoOz (442.70)
Lit: Allemand 1988
Me
22a-Hydroxystictan-3-one
(22a-Hydroxystictan-3-on)
Me
C30HsoOz (442.70) ( 3
.....
OHC 4
Me
CH 2 Me
23
Oil
IR (Nujol): 888, 1635, 1700, 3450cm-1
lH-NMR (CDCI3 ): 0.78 (3H,s,Me-28), 0.87
(6H,s,Me-27,Me-29), 0.99 (3H,s,Me-30), 1.03
(3H,s,Me-25), 1.06 (3H,s,Me-26), 1.80 (3H,s,
Prisms (n-hexane), mp 218-220 GC, crystals (ac-
Me-24) 3.15 (1H,d,J=10Hz,H-22), 4.82 (2H,bs,
etone), mp 216 GC, [apO n + 129 (CHCI3, c 1.00)
=CH z-23), 9.75 (lH,s,-CHO-3)
IR (KBr): 575, 588, 600, 620, 662, 715, 750, 765,
MS, m/z 442 (M+)
800, 824, 844, 860, 875, 900, 920, 962, 978, 990,
StL:' Pseudocyphellaria degelii D.Gall.
1012, 1020, 1030, 1050, 1080, 1100, 1132, 1172,
TLC: A: 67, B': 70, C: 56, E: 52, G: 76
1185, 1208, 1236, 1248, 1280, 1300, 1312, 1326,
Lit: Goh et al. 1979
1338, 1356, 1380, 1456, 1470, 1690, 1704, 2880,
2950, 351Ocm- 1
3.20 Terpenoids 379
22a-Hydroxy-3,4-secostict-4(23)-en-3-oic acid StL: Evernia prunastri (1.) Ach.

[22a-Hydroxy-3,4-secostict -4(23 )-en-3-saure] Lit: Allemand 1988
C30HS003 (458.70)
Lanosterol
Me
21 27
tvle Me
25
Me
26
Crystals (acetone), mp 235-23rC

IR (Nujol): 890, 1635, 1705, 2600-3200,
3430 cm-l Crystals, mp 138-144C, [ans + 60 (CHCI3)
MS, miz 458 (M+) UV (MeOH): 225, 243-254nm
Deriv: Methyl 22a-hydroxy -3,4-secostict-4( 23)- IR (KBr): 690, 1245, 1380, 1450-1480, 1620-
en-3-oate, crystals, mp 115-118C (acetone), 1670, 1720, 2850, 2960, 3400 cm- 1
from 22a-hydroxy-3,4-secostict-4(23)-en-3-oic IH-NMR (200MHz,CDCI3): 0.70 (3H,s,Me-18),
acid with CH1N1 0.82 (3H,s,-Me), 0.92 (3H,d,Me-21), 1.10, l.l5,
IH-NMR (CDCI3): 1.78 (3H,s,Me-24), 3.15 (lH, 1.17 (3x3H,3xs,3x-Me), 2.10-2.17 (6H,d,Me-26,
s,H-22), 3.65 (3H,s,-COOMe), 4.88 (2H,bs, Me-27), 1.22-1.65 (23H,m,-CHz-,-CH=), 3.95
=CH l -23) (1H,s,H-3), 6.25 (1H,H-24)
StL: Pseudocyphellaria degelii D.Gall. MS, miz 426 (M+,28%), 393 (7),383 (7), 355 (2),
TLC: A: 52, B': 54, C: 51, E: 11, G: 62 313 (6),301 (3),299 (2), 287 (8), 271 (6),269 (16),
Lit: Goh et al. 1979 257 ell), 256 (11), 255 (16), 229 (14),218 (33),
207 (20),205 (34), 203 (38), 191 (37), 189 (41),
175 (25), 161 (30), 149 (28), 136 (67), 120 (61),
Isomultiflorenone (Isomultiflorenon) 109 (68), 107 (81), 96 (100)
C30H 4S O (424.68) Deriv: Acetyllanosterol, mp 130C, [an4 + 60
(CHCI3), from lanosterol with ACzO-pyridine
StL: Evernia prunastri (1.) Ach., Usnea
articulata (1.) Hoffm.
Lit: Nicollier et al. 1979b; Ali 1992
Leucotylic acid (Leucotylsaure)

C30HS004 (474.70)
Me
Crystals (acetone), mp 188-195C, [ali? + 69.1

(CHCI3, c 1.08)
MS, miz 424 (M+), 409, 257, 245, 218, 205, 109,
95
Plates (MeOH), mp 259-260 DC, [al D + 330 (43),97 (36), 95 (68),93 (60),83 (47),81 (73),79
(CHCI3, c 0.15) (44),69 (100), 67 (55), 59 (83), 55 (89),43 (94),41
IR (Nujol): 1690, 1710,3200, 3380cm-1 (80)
Deriv: Methyl leucotylate, plates (EtOH), mp Deriv: 6,16-Di-O-acetylleucotylin, needles
298-301 DC, [al D + 29 (CHCI 3, c 2.0), from (MeOH), mp 241-242 DC, [al D + 120, from
leucotylic acid in EtOH with CHzNz at 5 DC in 1 leucotylin with AczO-pyridine at 20 DC in 24 h
day StL: Lecanora muralis (Schreb.) Rabenh.,
lH-NMR (60MHz,CDCI3): 0.78 (3H,s,Me-28), Myelochroa leucotyliza (Nyl.) Elix et Hale
0.86 (3H,s,Me-25), 0.99 (3H,s,Me-27), 1.05 (3H, TLC: A: 17, Bf: 28, C: 21, E: 14, G: 30
s,Me-26), 1.16 (6H,s,Me-24,Me-29), 1.28 (3H,s, MC: Fig. 56B,C
Me-30), 3.68 (3H,s,-COOMe), 4.10 (1H,m, Lit: Yosioka and Nakanishi 1963; Yosioka et al.
H-16) 1968a,1969a
MS, m/z 488 (M+,4%), 470 (8),452 (6),428 (2),
235 (78), 223 (24), 205 (83), 187 (28), 175 (61),
Lupeol
121 (100)
StL: Myelochroa leucotyliza (Nyl.) Elix et Hale C30HSOO (426.70)
TLC: C: 37, E: 2, G: 32
Lit: Yosioka et al. 1966b,1972b
Leucotylin
C30Hs203 (460.72)
Needles (EtOH), mp 212-216 DC, [ana + 28

(CHCI3)
IR (KBr): 1110-1140, 1380, 1460, 1620, 2860,
2920, 3400 cm- 1
Needles (MeOH), mp 335-336 D, [ana + 56.5 lH-NMR (200MHz,CDCI3): 0.73, 0.85, 0.90, 0.92,
(CHCI3, c 0.566) 0.98, 1.05, 1.10, 1.60 (8x3H,8xs,8x-Me), 3.65
IR (KBr): 770,840,870,902,960,985,1030,1062, (1H,t,H-3), 4.55, 4.68 (2H,m,=CH 2-29).
1160, 1230, 1260, 1390, 1450, 2940, 3250, 13C-NMR (25.15MHz,CDCI3): C-l: 38.7, C-2:
3400cm-1 27.5, C-3: 79.0, C-4: 38.9, C-5: 55.3, C-6: 18.3,
lH-NMR (60MHz,CDCIJ: 0.75, 0.83, 0.96, 1.03, C-7: 34.3, C-8: 40.9, C-9: 50.5, C-10: 37.2, C-11:
1.04, 1.14, 1.22 (24H,7xs,8x-Me), 4.01 (2H,m, 21.0, C-12: 25.2, C-13: 38.1, C-14: 42.9a , C-15:
H-6,H-16) 27.5, C-16: 35.6, C-17: 43.0., C-18: 48.0b , C-19:
MS, m/z 460 (M+,l %), 442 (13), 424 (27), 406 48.3 b, C-20: 150.9, C-21: 29.9, C-22: 40.0, C-23:
(11),399 (11),391 (9),381 (7),359 (6),341 (7), 28.0, C-24: 15.3, C-25: 16.1 c, C-26: 16.0c, C-27:
329 (6), 207 (15), 205 (15),190 (15),189 (27), 187 14.6, C-28: 18.0, C-29: 109.3, C-30: 19.3. Values
(25), 175 (12), 173 (12), 163 (15), 161 (19), 159 marked with a, b, and c may be exchanged
(14), 151 (47), 147 (37), 135 (36), 133 (35), 123 MS, m/z 426 (M+,14%), 411 (4),383 (1),218 (30),
(62), 121 (48), 119 (46), 109 (67), 107 (57), 105 207 (10),206 (1), 204 (7), 2(f3 (6), 189 (20), 149
3.20 Terpenoids 381
(17), 135 (11), 125 (17), 121 (11), 111 (29), 109
(23),107 (11), 97 (58), 83 (86), 69 (88), 57 (87), 55
(88), 43 (100)
Deriv: Acetyllupeol, mp 213-220C, [a]D + 45
(CHCI3), from lupeol with Ac20-pyridine MeOCO
Me" Me
StL: Flavocetraria nivalis (1.) Karnef. et TheIl
Needles (MeOH-H 20), mp 255-255.5C, [a]D +
TLC: A: 60, B': 70, C: 56, E: 52, G: 70
39.2 (CHCI3, c 1.00)
Lit: Bruun 1969; Nicollier et aL 1979b; Sholichin
IR (KBr): 1250, 1695, 1728,3450 cm-1
et aL 1980
MS, m/z 530 (M+,6%), 515 (1),470 (7),437 (4),
428 (19),411 (5), 367 (28),251 (100),249 (11),
Lupeone, Lup-20(29)-en-3-one 233 (33), 189 (51)
[Lupeon, Lup-20(29)-en-3-on] StL: Pyxine endochrysina NyL
Lit: Yosioka et aL 1972c
C30H 4s O (424.70)
Methyl pyxinate (Pyxinsauremethylester)

C31Hs204 (488.73)
29
... )~COOMe
I'OH
Me
HO
Me'" Me
Me Crystals (MeOH), mp 282-284C, [a]D + 39.5

(CHCI3, c 0.88)
Crystals (EtOH), mp 160C, [an; + 60 (CHCI3, c IR (KBr): 1250, 1713cm-1
0.54) MS, m/z 488 (M+,2%), 470 (2),455 (3),437 (3),
lH-NMR (CDCI3): 0.70, 0.84 (2x3H,2xs,2x-Me), 429 (3),385 (14),367 (15), 251 (100),233 (39),
1.65 (3H,s,Me-30), 4.48 (lH,d,J=2Hz,H-29), 207 (33), 189 (40)
4.60 (1H,d,J=2Hz,H-29) StL: Pyxine endochrysina NyL
MS, m/z 242 (M+,37%), 409 (12), 381 (4), 218 Lit: Yosioka et aL 1972c
(31),205 (100),204 (31), 203 (29), 189 (39)
StL: Cladonia macaronesica Ahti, Evernia
Moretenone, Hop-22(29)-en-3-one
prunastri (1.) Ach.
[Moretenon, Hop-22(29)-en-3-on]
Lit: Allemand 1988; Gonzalez et aL 1991;
Shiojima et aL 1992 C30H 4S O (424.68)
MethyI3-0-acetylpyxinate
(3-0-Acetylpyxinsauremethylester)
C33Hs40S (530.76)
o
Crystals, mp 190-204C, [an; + 50 (CHCl3, c 30-Nor-21a-H-hopan-22-one,Iso-adiantone

0.03) (30-Nor-21a-H-hopan-22-on, Iso-adianton)
IR (KBr): 1380, 1410, 1650, 1725, 2800-
C29 H 4S O (412.37)
2940cm- 1
lH-NMR (200MHz,CDCl3): 0.72 (3H,s,Me-28),
0.95 (3H,s,Me-25), 0.97 (3H,s,Me-27), 1.03
(6H,s,Me-24,Me-26), 1.09 (3H,s,Me-23), 1.20-
1.90 (25H,m), 2.12 (3H,s,Me-30)
MS, m/z 424 (M+,46%), 409 (20), 381 (3),368 (6),
205 (33),204 (20), 190 (26), 189 (100), 119 (30),
105 (33)
Lit: Nicollier et al. 1979b Crystals (acetone), mp 234-235C, [al D + 2.3
(CHCl3)
IR (KBr): 1350, 1365, 1380, 1445, 1465, 1702,
30-Nor-21a-H-hopan-3,22-dione
2865, 2945 cm- 1
(30-Nor-21a-H -hopan-3,22-dion)
lH-NMR (100MHz,CDCl3 ): 0.70 (3H,s,Me-28),
C29H4602 (426.66) 0.80 (3H,s,Me-25), 0.83 (3H,s,Me-24), 0.85 (3H,
s,Me-23), 0.96 (3H,s,Me-27), 0.98 (3H,s,Me-
26),2.13 (3H,s,Me-29)
MS, m/z 412 (M+,57%), 397 (14), 369 (5), 206
Me (13),191 (100), 177 (8), 149 (39),43 (64)
29 Deriv. 2.4-Dinitrophenylhydrazone of 30-
nor-21a-H-hopan-22-one, mp 247-248 DC, from
30-nor-21a-H-hopan-22-one with 2.4-dinitro-
Crystals, mp 262.5 DC, [altf + 23.5 (CHCl3, c 0.85) phenylhydrazine
IR (KBr): 1360-1380, 1440-1460, 1698-1708, StL: Platismatia glauca (1.) W.Culb. et C.Culb.
2850-2950 cm- 1 Lit: Hveding-Bergseth et al. 1983
lH-NMR (100MHz,CDCl3): 0.72 (3H,s,Me-28),
0.95 (3H,s,Me-25), 0.97 (3H,s,Me-27), 1.03
(6H,s,Me-24,Me-26), 1.09 (3H,s,Me-23), 2.12 Phlebic acid A (Phlebsaure A)
(3H,s,Me-29) C32Hs20S (516.74)
MS, m/z 426 (M+,3%), 411 (1),383 (0.5),265 (2),
220 (1), 206 (5),205 (6), 191 (15), 189 (45), 177
(2),149 (10), 97 (35),85 (49),83 (35),81 (35),57
(93),55 (55),43 (100),41 (60)
TLC: A: 70, B': 59, C: 59, E: 58, G: 54
Lit: Nicollier et al. 1979b
Crystals (MeOH-H 20), mp 243-245C, [al D

+ 70.2 (CHCl3, c 0.79)
IR (KBr): 1265, 1703, 1717, 1742, 3470cm-1
3.20 Terpenoids 383
IH-NMR (l00MHz,CDCI3): 0.84, 0.95,1.09,1.13,

1.24 (l8H,5xs,6x-Me), 2.02 (3H,s,-OCOMe), "'~.k"Me
4.25, 4042 (2H,2xd,J=12Hz,-CH 2-28) I 'OH
MS, m/z 516 (M+), 498, 456, 443, 438, 425, 221, Me
203,189,59
Deriv: Methyl phlebate A, mp 191-192.5C
(MeOH), from phlebic acid A with CH 2N l Me
TLC: A: 38, B': 35, C: 40, E: 8, G: 45 Crystals (CHCI 3-MeOH), mp 265-271 c, [aW +
Lit: Takahashi et al. 1969 28.2 (CHCI3, c 0.35)
IR (KBr): 1690, 1710, 3450cm-1
IH-NMR: 0.70, 0.79, 0.91, 1.15, 1.19, 1.32, 1.38
Phlebic acid B (Phlebsaure B) (21H,7xs,7x-Me)
C30HS003 (458.70) MS, m/z 458 (M+), 443, 440, 425, 397, 221, 219,
205,202, 191 (100%), 149,59
Deriv: Methyl phlebate C, mp 195-197C (ac-
etone-H20), from phlebic acid C with CH 2N2
Lit: Bachelor et al. 1990
Phlebic acid D (Phlebsaure D)

Crystals (CHCI3-MeOH), mp 258-260 c,. [am + C32HszOs (516.74)
52.9 (pyridine, c 0.59)
IR (KBr): 1705, 1715, 3480cm-1
IH-NMR (lOOMHz,CDCU: 0.85 (3H,s,Me-25),
0.92, 0.98, 1.33, 1.38, 1.26 (l8H,5xs,6x-Me)
MS, m/z 458 (M+), 440, 415, 387, 361, 261, 221,
207, 189
Deriv: Methyl phlebate B, mp 231-233C 7 OCOMe
(CHC13-MeOH), [aJ] + 54.3 (CHCI3, c 0040),
from phlebic acid B with CH l N 2
Crystals (CHCI3-MeOH), mp 235-240 c, [anZ +
23.9 (CHCI3, c 0.70)
TLC: A: 44, B': 42, C: 48, E: 26, G: 50
IR (KBr): 1235, 1740, 1750,3400, 3550cm-1
Lit: Takahashi et al. 1970
IH-NMR (pyridine-ds): 0.69, 0.75, 0.90, 1.28,
1.20, 1.33, 1.37 (7x3H, 7xs,7x-Me), 2.10 (3H,s,
Phlebic acid C (Phlebsaure C) -OCOMe), 2.82 (lH,d,J=14Hz), 5.08 (lH,dd,J=
1204Hz)
C30HS003 (458.70) MS, m/z 516 (M+), 498, 474, 456, 441, 438, 423,
413,398,395,218,217,203,191,190,189 (100%),
59
Deriv: Methyl phlebate D, mp 230-231C
(MeOH), from phlebic acid D with CH1N 1
StL: Peltigera aphthosa (1.) Willd. Deriv: Triacetylpyxinol, needles (MeOH-HzO),

Lit: Bachelor et al. 1990 mp 180-181C, from pyxinol with ACzO-tolu-
ene-p-sulphonic acid at 28C in 20 h
StL: Pyxine endochrysina Nyl.
Pyxinic acid (Pyxinsaure)
Lit: Yamauchi et al. 1969; Yosioka et al. 1972c
C30HS004 (474.70)
Retigeric acid A (Retigersaure A)
C30H4S04 (472.68)
Crystals, mp 254-255C, [a]D + 62 (EtOH, c 0.3)

IR (Nujol): 1705, 3500, 3560 cm- 1
Deriv: Methyl 3-0-acetylpyxinate, mp 257C,
from pyxinic acid with CH 2Nz and subsequent Crystals (EtOAc-MeOH-Hp), mp 296-299C,
acetylation with ACzO-pyridine [a]D + 26.5 (pyridine, c 0.77)
lH-NMR (60MHz,CDCl3): 0.81, 0.84, 0.92, 0.94, IR (KBr): 790, 826, 904, 954, 966, 1006, 1048,
1.30 (21H,5xs,7x-Me), 2.03 (3H,s,-OCOMe), 1244, 1372, 1440, 1462, 1690,2990, 3500cm-1
3.73 (3H,s,-COOMe), 4.50 (1H,q,H-3) Deriv: Methyl retigerate A, mp 259-261 C (ac-
StL: Pyxine endochrysina Nyl. etone), from retigeric acid A with CHzNz
Lit: Yosioka et al. 1966a lH-NMR (100MHz,CDCl3): 0.72 (3H,s,Me-26),
0.75 (3H,s,Me-28), 0.81 (3H,s,Me-27), 0.82, 0.88
Pyxinol (2x3H,2xd,Me-29,Me-30), 1.16 (3H,s,Me-25),
1.24 (3H,s,Me-24), 3.75 (3H,s,-COOMe)
C30Hsz04 (476.72) MS, m/z 486 (M+,38%), 471 (100),453 (21),435
(11),426 (8),411 (17),393 (17),375 (8),365 (9),
333 (22), 319 (78), 307 (23), 301 (23),283 (17),
259 (16),241 (44),205 (21)
StL: Lobaria retigera (Bory) Trev.
MC: Fig. 56D
Lit: Takahashi et al. 1972a
Needles (MeOH-HzO), mp 225-226C, [a]D +

62.8 (CHCl3, c 0.99) Retigeric acid B (Retigersaure B)
IR (CCl4 ): 3430, 3600cm-1 C30H4606 (502.67)
lH-NMR (60MHz,CDCIJ: 0.80 (3H,s,Me-28),
0.89 (3H,s,Me-19), 0.94 (3H,s,Me-30), 1.01 (6H,
s,Me-18,Me-29), 1.13 (3H,s,Me-21), 1.30 (6H,s,
Me-26,Me-27), 3.27 (1H,m,H-3), 3.56 (1H,m,
H-12), 3.87 (1H,t,J=7Hz,H-24)
MS, m!z463 (1%),417 (4), 400 (68),381 (27),207
(50),189 (25), 143 (100)
3.20 Terpenoids 385
Amorphous powder (MeOH-H 20), mp > 268C 119 (42), 109 (70), 107 (60),95 (87),93 (63),81
IR (KBr): 670, 910, 960, 1010, 1048, 1116, 1220, (87), 69 (82), 55 (75), 43 (87)
1372, 1450, 1462, 1690,2990, 3500cm-1 Deriv: Stictan-3,22-dione, mp 241-242C (ac-
Deriv: Dimethyl diacetylretigeranate B, mp etone), from stictan-3J3,22a-diol by oxidation
180-181C (MeOH-H 20), [a]D - 31.0 (CHCI3 , c with Jones' reagent
0.81), from retigeric acid B with CH 2N2 and sub- StL: Pseudocyphellaria durvillei (Del.) Vain.,
sequent acetylation with Ac20-pyridine Pseudocyphellaria flavicans (Hook. et TayI.) Vain.
IH-NMR (100MHz,CDCI3): 0.69 (3H,s,Me-26), TLC: A: 44, B': 47, C: 43, E: 29, G: 62
0.77 (3H,s,Me-28), 0.82 (3H,s,Me-27), 0.84, 0.90 Lit: Rao and Seshadri 1968; Chin et aI. 1973
(2x3H,2xd,Me-29,Me-30), 1.08 (3H,s,Me-24),
1.97, 2.00 (2x3H,2xs,2x-OCOMe), 3.68 (6H,s,
Stictan-2a,3 ~,22a- triol
2x-COOMe), 5.58 (1H,bs,H-11)
StL: Lobaria retigera (Bory) Trev. C30H sP3 (460.72)
MC: Fig. 57A
Lit: Takahashi et al. 1972a Me
Stictan-3~,22a-diol, Retigeradiol
C30Hs202 (444.72)
Me
Crystals (acetone), mp 276C, [am + 15.2

(CHCIJ
IR (Nujol): 3340-3500 cm- 1
Deriv: 2a,3~,22a- Triacetoxystictane, mp 274C
(acetone), from stictan-2a,3~,22a-triol with
Ac2 0-pyridine
Crystals (CHCI3-acetone), mp 283C, [am + StL: Pseudocyphellaria flavicans (Hook. et TayI.)
12.3 (CHCI3, c 1.10) Vain.
IR (KBr): 600, 615, 645, 690, 724, 745, 826, 854,
926,962,996,1014,1060,1074,1096,1130,1170,
1194, 1250, 1374, 1455, 256~ 2860, 2920,
3460cm-1 Taraxer-14-ene (Taraxer-14-en)
IH-NMR (100MHz,CDCI3): 0.73 (3H,s,Me-28),
C30HSO (410.70)
0.78 (3H,s,Me-24), 0.87 (3H,s,Me-29), 0.90 (6H,
s,Me-25,Me-27), 0.97 (6H,s,Me-23,Me-30),
1.14 (3H,s,Me-26), 3.14 (lH,d,H-22), 3.26 (1H,
m,H-3)
MS, m/z 444 (M+,9%), 440 (11),429 (5),426 (23),
425 (ll), 411 (12),409 (7), 383 (7),365 (4),315
(5), 290 (5), 275 (ll), 257 (7), 247 (7), 234 (15),
219 (13),208 (20), 207 (87),205 (40), 191 (40),
190 (40), 189 (100), 175 (23), 163 (25), 161 (28),
149 (34), 136 (48), 135 (70), 123 (57), 121 (70), Me
Crystals, mp 238-239 DC, [a] + 3 (CHCl3 ) IH-NMR (CDCl3): 0.83, 0.91, 0.95,1.06,1.08,1.13
StL: Cladonia deformis (L.) Hoffm. (24H,6xs,8x-Me), 5.55 (lH,dd,Jl=4.0,J 2=7.0Hz,
Lit: Bruun 1954b H-15)
MS, m/z 424 (M+,lOOO/O), 409 (51), 300 (97), 285
(62),204 (90), 189 (40)
Taraxerol
StL: Cladonia macaronesica Ahti
Lit: Gonzalez et aL 1991
2a)3~)22a- Triacetoxystictane
(2a,3~,22a- Triacetoxystictan)
C36 H ss 06 (586.82)
Me
MeOCO.
'2
Crystals, mp 280-282 DC, [alii' - 6.97 (CHCl3, c
0.86) MeOCO 3
Me" Me
IR (CHCl3): 1380, 1450, 1600, 2850-2920, 3600-
3670cm-1 Crystals (acetone), mp 274 D C, [am - 55.1
IH-NMR (100MHz,pyridine-d s): 0.90, 0.96, 0.98, (CHC13, c 0.88)
1.04, 1.11, 1.20, 1.30 (24H,7xs,8x-Me) IR (Nujol): 1240, 1730 cm- 1
MS, mlz 426 (M+'220/0), 411 (11), 392 (2), 302 IH-NMR (100MHz,CDCl3): 0.81, 0.85, 0.89, 0.93,
(39), 287 (36), 284 (6), 269 (17), 257 (12), 204 1.02, 1.15 (24H,6xs,8x-Me), 1.97 (3H), 2.03
(100), 189 (35), 149 (55), 135 (59), 133 (54), 121 (2x3H,2xs,3x-OCOMe), 4.69 (IH,d,H-3), 4.74
(57), 109 (61), 107 (55), 95 (66),81 (59),69 (69) (lH,d,H-22), 5.16 (lH,sextet,H-2)
StL: Evernia prunastri (L.) Ach. Deriv: Stictan-2a,3~,22a-triol, mp 276 DC (ac-
Lit: Nicollier et al. 1979b etone), [an + 15.2 (CHCU, by saponification of
2a,3~,22a-triacetoxystictane with KOH-MeOH
Taraxerone (Taraxeron)
Vain.
Lit: Chin et aL 1973
Me
Ursolic acid (Ursolsaure)
C30H4S03 (456.69)
Crystals, mp 240-242 DC, [a n + 12.5 (CH Cl3, c

1.03)
3.20 Terpenoids 387
Needles (EtOH), mp 280-292 DC, [a]D + 72 IR (KBr): 764, 835, 862, 898, 944, 990,1028,1040,
(CHC1 3 ) 1050, 1070, 1135, 1154, 1210, 1250, 1262, 1300,
IR (KBr): 674, 750, 776, 824, 846, 900, 930, 962, 1360, 1388, 1470,2980, 3380cm-1
984, 1006, 1048, 1100, 1108, 1140, 1188, 1250, lH-NMR (60MHz,CDC13 ): 0.75 (3H,s,Me-28),
1288, 1314, 1390, 1460, 1700, 2960, 3200, 0.86 (3H,s,Me-25), 1.00 (3H,s,Me-27), 1.04
3500cm-1 (3H,s,Me-26), 1.17 (9H,s,Me-23,Me-29,Me-30)
lH-NMR (200MHz,CDC13 ): 0.83, 0.86, 0.87, 0.95, MS, m/z 444 (M+,35%), 426 (7),411 (3),385 (7),
1.01, 1.03, 1.08 (21H,7xs,7x-Me), 1.81 (lH,bd, 308 (7), 207 (100), 203 (14), 191 (36), 190 (35),
H-18), 3.22 (1H,bt,H-3), 5.17 (1H,bt,H-12) 189 (90), 177 (9),175 (9), 163 (19), 161 (18), 149
13C-NMR (CDC1 3 ): C-1: 38.87, C-2: 27.54, C-3: (74), 148 (22), 147 (23), 135 (25), 121 (30), 119
78.96, C-4: 41.65, C-5: 45.45, C-6: 18.3, C- (24), 109 (39), 107 (30), 95 (81), 93 (32), 83 (12),
7: 33.0, C-8: 41.3, C-9: 46.83, C-1O: 38.24, C-ll: 81 (44),78 (86),69 (76), 59 (93),55 (41),43 (33),
23.81, C-12: 124.58, C-13: 138.2, C-14: 41.32, C- 41 (32)
15: 29.01, C-16: 26.98, C-17: 47.02, C-18: 39.28, Deriv: 6-0-Acetylzeorin, prisms (acetone), mp
C-19: 38.39, C-20: 38.4, C-21: 26.98, C-22: 221-226 DC, [an + 78.1 (CHC13, c 0.64), from
38.51, C-23: 15.22, C-24: 13.95, C-25: 17.02, C- zeorin with Ac10-pyridine at 80 DC in 2h
26: 16.84, C-27: 25.6, C-28: 178.30, C-29: 18.00, StL: Lecanora muralis (Schreb.) Rabenh.,
C-30: 16.02 Parmelia leucotyliza (Nyl.) Elix et Hale
MS, m/z 456 (M+,4%), 438 (6),423 (3),410 (3), TLC: A: 52, B: 42, B': 43, C: 43, E: 19, F: 74, G: 50
393 (3),249 (20), 248 (100),207 (16),204 (8), 203 MC: Fig. 57D
(60),202 (4), 190 (8), 189 (20), 175 (4), 173 (3), Lit: Yosioka et al. 1967, 1968a, 1969b, 1971b,
150 (3), 149 (16), 133 (32), 121 (12), 119 (16),95 1972a; Nakanishi et al. 1971
(12), 81 (16), 69 (20), 67 (8), 59 (20), 57 (25), 55
(20), 44 (16)
Deriv: Methyl ursolate, needles, mp 169-170 DC, Zeorinone (Zeorinon)
[a]D + 62 (CHC1 3), from ursolic acid with CH1N 1
StL: Evernia prunastri (1.) Ach., Flavocetraria
nivalis (1.) Karnef. et Thell
TLC: A: 52, B: 50, B': 54, C: 49, E: 25
MC: Fig. 57B,C
Lit: Bruun 1969; Nicollier 1979
Zeorin
Needles (CHC13-MeOH), mp 251-255 DC, [am +

25.2 (CHC1 3, c 0.39)
lH-NMR (300MHz,CDCU: 0.75 (3H,s,Me-28),
0.79 (3H,s,Me-25), 0.87 (3H,s,Me-23), 0.91 (1H,
H-19P), 0.93 (3H,s,Me-26), 0.98 (lH,H-la),
1.04 (3H,s,Me-27), 1.05 (lH,H-3a), 1.08 (lH,
Double pyramids or hexagonal plates (CHC13 - H-15a), 1.15 (3H,s,Me-29 or Me-30), 1.18, (3H,
EtOH), mp 236-242 DC, [am + 63.3 (CHC1 3, c s,Me-29 or Me-30), 1.19 (3H;s,Me-24), 1.24
0.56) (lH,H-3P), 1.34 (lH,H-13P), 1.36 (2H,H-lla,
H-15~), 1.39 (lH,H-2a), 1.41 (lH,H-i7~), 1.47 Deriv: Acetylbrassicasterol, mp 152-159C,

(2H,H-12a,H-20~), 1.50 (IH,H-12~), 1.52 (IH, [am - 64 (CHCI3 , C 1.0), from brassicasterol
H-19a), 1.54 (lH,H-2~), 1.56 (IH,H-16a), 1.62 with Ac2 0-pyridine
(IH,H-ll~), 1.71 (IH,H-1~), 1.74 (lH,H-20a), StL: Cladonia sulphurica (Michx.) Fr., Xan-
1.77 (lH,H-9a), 1.78 (lH,H-7~), 1.93 (IH,H- thoria parietina (L.) Th.Fr.
16~), 2.05 (lH,H-5a), 2.19 (lH,H-21~), 2.46 Lit: Lenton et al. 1973a; Bruun 1976a
(lH,H-7a).
!3C-NMR (75MHz,CDCI3 ): C-1: 41.1, C-2: 18.6,
Campesterol
C-3: 42.8, C-4: 32.6, C-5: 66.5, C-6: 214.0, C-7:
51.7, C-8: 48.5, C-9: 50.9, C-10: 44.1, C-ll: 21.6,
C-12: 24.0, C-13: 49.8, C-14: 42.4, C-15: 34.5,
C-16: 22.0, C-17: 54.2, C-18: 44.1, C-19: 41.5,
C-20: 26.8, C-21: 51.2, C-22: 73.8, C-23: 32.7, Me
C-24: 22.0, C-25: 17.2, C-26: 17.0, C-27: 17.8,
C-28: 16.3, C-29: 29.0, C-30: 31.2
MS, miz 442 (M+,13%), 427 (5),424 (10), 409 (7),
384 (26),245 (5),207 (48),205 (34), 189 (86),149 HO
(IOO)
Deriv: Zeorininone, plates (EtOH), mp 177- Crystals, mp 152-158 DC, [anO - 35 (CHCI3, c 1.0)
178C, [aU? + 29.8 (CHCI3, c 1.04), from MS, miz 400 (M+), 385, 382, 367, 315, 289, 273,
zeorinone with AcOH-H 2S04 at 20C in 24h 213
StL: Rinodina thiomela (Nyl.) Miill.Arg. Deriv: Acetylcampesterol, mp 137-140C, [an
TLC: A: 54, Bf: 53, C: 49, E: 40, G: 64 - 38 (CHCI 3 , c 1.0), from campesterol with Ac 2 0-
Lit: Schmidt and Huneck 1979; Wilkins et al. pyridine
1989a StL: Xanthoria parietina (L.) Th.Fr.
Lit: Lenton et al. 1973a; Huneck et al. 1995b
3.20.6
Steroids
Cerevisterol
Brassicasterol
Me
HO
HO
Needles (CHCI3 -MeOH), mp 256-259C, laW
- 79.9 (pyridine, c 1.35)
Crystals, mp 157-158C, laW - 62 (CHCI3, c lH-NMR (200MHz,CDC1 3 ): 0.63 (3H,s,-Me),
1.00) 0.84 (3H,d,J=6.9Hz,-Me), 0.85 (3H,d,J=6.7Hz,-
MS, miz 398 (M+), 380, 300, 271, 255, 213 Me), 1.04 (3H,d,J=7.2Hz,-Me)~ 1.07 (3H,s,-Me),
3.20 Terpenoids 389
J.57 (IH,d,J=5Hz,H-6), 3.98 (IH,m,H-3), 5.21 Cholesterol

(2H,m,H-22,H-23), 5.29 (IH,d,J=5.0Hz,H-7)
C27 H 460 (386.64)
MS, m/z 430 (M+,2%), 412 (85), 397 (29), 394
(53), 384 (17), 383 (56),380 (31), 379 (91),365 Me
(10), 269 (30),251 (38), 159 (18), 107 (22)
Deriv: Diacetylcerevisterol, needles (MeOH),
mp 163-165C, [a]] - 140 (CHCI3 , c 0.26), from
cerevisterol with Ac2 0-pyridine
StL: Ramalina hierrensis Krog et 0sth. HO
Lit: Gonzalez et al. 1992b
Plates (EtOH), mp 145-151C, [an - 39.5
(CHCI3, c 1.0)
Cholesta-3,5-dien-7 -one React: Liebermann-Burchard test (Ac 20-H 2S0 4
(Cholesta -3,5-dien -7 -on) cone.) red ---7 violet ---7 green
lH-NMR (400MHz,CDCI3): 0.79, 0.82,0.85,0.90,
C27H4zD (382.61) 0.95 (15H,m,5x-Me), 1.01-1.99 (-CHn=CH-),
2.27 (IH,m,H-20), 3.52 (1H,bd,H-3), 5.33
Me
(lH,m,H-6)
MS, m/z 386 (M+,4%), 371 (6), 356 (5), 355 (4),
344 (17), 315 (7),301 (5),300 (3),285 (10),284
(23), 275 (10), 273 (14),259 (27), 256 (31), 255
3 (7), 250 (58), 247 (13), 233 (44), 219 (22), 218
(22),217 (38), 213 (20),207 (15),205 (17),203
Crystals, mp 111-115C, [a]D - 310 (CHCI3 ) (22), 191 (31), 189 (20), 177 (30), 167 (36), 163
StL: Umbilicaria cylindrica (1.) DeL ex Duby (40), 153 (100), 151 (98)
Lit: Huneck et al. 1995b Deriv: Acetylcholesterol, mp 111-116C, [anO -
45 (CHCI3, c 1.0), from cholesterol with AczO-
pyridine
Cholestan-3B-ol
C27 H 4S O (388.65) Lit: Lenton et aL 1973a
Me
Clionasterol
HO
Crystals, mp 121-126 C, [an + 23 (CHCI3, c 1.0)

Deriv: Acetylcholestan-3B-ol, mp 91-111 C,
[an + 13 (CHCI3, C 1.0), from cholestan-3~-ol
with Ac 20-pyridine HO
MS, m/z 430 (M+), 370, 276, 257, 230, 215
StL: Pseudevernia furfuracea (1.) Zopf Crystals, mp 141-150C, [ano-43 (CHCI3 , c 1.0)
Lit: Wojciechowski et al. 1973 MS, m/z 414 (M+), 396, 381, 329; 303, 273, 213
Deriv: Acetylclionasterol, mp 130-144 DC, [a no-

43.5 (CHC1 3, c 1.0) Me-
Lit: Lenton et al. 1973a
Episterol H0
C2s H460 (398.65) Crystals, mp 173.5-174C,[a]D - 23.4 (CHC13 )

MS, m/z 380, 342, 313, 288, 255, 227, 213, 189,
161
Me- StL: Cetrariella delisei (Bory ex Schaer.) Karnef.
Lit: Solberg 1987
Ergosta-7,24( 28 )-dien-3 ~-ol

HO
CZS H46 0 (398.65)
Crystals, mp 131C, [a]g + 6 (CHC1 3, c 2.0)
MS, m/z 398 (M+), 383, 314, 271, 255, 213
Deriv: Acetylepisterol, mp 161-162C, [a]D - 4
Me
(CHC1 3, C 1.0), from episterol with Ac2 0-pyri-
dine
StL: Lobaria pulmonaria (1.) Hoffm., Xanthof'ia
parietina (1.) Th.Fr.
Lit: Barton et al. 1972; Lenton et al. 1973a;
Solberg 1987
Crystals (MeOH), mp 127.5-128.5C, [a]D + 4.4
(CHC1 3, c 2.3)
Ergosta-3,S-dien-7-one (Ergosta-3,5-dien-7-on) StL: Umbilicaria cylindrica (1.) Del. ex Duby
CZSH440 (396.63) Lit: Huneck et al. 1995b
Ergo sta-4,6,8,11,22-pentaen -3 ~-ol

Me-
CZS H 40 0 (392.60)
3 Me
Me
StL: Umbilicaria cylindrica (1.) Del. ex Duby
Ergosta -7,22-dien-3~-ol, dihydroergosterol

CZS H 46 0 (398.65) Lit: Huneck et al. 1995b
3.20 Terpenoids 391
Ergosta-5,7,9 ( 11 ),22-tetraen -3B-ol Ergost-5-en-3B-ol

C2s H 42 0 (394.62) C2s H 4S O (400.66)
Me
Me Me
HO
StL: Cladonia rangiformis Hoffm. Crystals, mp 157-158C, [an4 - 45.5 (CHCI 3 , c

Lit: Delseth et aL 1979; Huneck and Schmidt 1.5)
1995 MS, m/z 400 (M+), 385, 382, 367, 315, 289, 273,
213
Ergosta-5,7,14,22-tetraen -3B-ol Lit: Lenton et aL 1973a
C2s H 42 0 (394.62)
Ergosterol
Me C28 H 44 0 (396.63)
Me
HO
Crystals, mp 198-201 C (dec.), [al D - 396 (CCI 4 )
MS, mlz 376, 361, 251, 235, 209, 181, 157, 143 HO
StL: Usnea hirta (1.) Wigg.
Lit: Solberg 1987 Crystals, mp 160-163 DC, [am - 131 (CHCI 3 , c
1.0)
UV (EtOH): 252 (3.58), 262 (3.84), 271 (4.00),
Ergosta-5,7,9(11)-trien-3B-ol
282 (4.02),293 (3.78),325 (1.56), 337.5nm (1.41)
C2s H 440 (396.63) lH-NMR (200MHz,CDCI 3 ): 0.82 (3H,s,Me-18),
0.84 (3H,s,Me-19), 0.86 (3H,d,Me-21), 0.91-
tyle 0.94 (6H,d,Me-26,Me-27), 1.04 (3H,d,Me-28),
Me 2.26 (lH,m,H-20), 3.63 (1H,m,H-3), 5.17-5.21
(2H,m,H-22,H-23), 5.39 (1H,dd,H-6), 5.57 (IH,
dd,H-7)
MS, mlz 396 (M+,1000/0), 367 (5), 337 (18), 271
HO (l0), 253 (18),211 (1O), 171 (20), 170 (l3), 149
(20), 143 (25), 125 (8)
StL: Umbilicaria cylindrica (1.) DeL ex Duby Deriv: Acetylergosterol, plates (Et2 0-MeOH),
Lit: Huneck et aL 1995b mp 171-181 DC, [an -90 (CHCI;, c 1.0)
StL: Cladonia rangiferina (L.) G.Web. ex Wigg.,

Xanthoria parietina (L.) Th.Pr. Me
TLC: A: 56, B: 66, B': 66, C: 43, E: 41, G: 59
MC: Pig. 65A,B
Lit: c.P. Culberson 1969; Lenton et aL 1973a
HO
Ergosterol-5a,8a-peroxide
Crystals, mp 132-145 DC, [am+ 25 (CHCI3, c 1.0)
(Ergosterol-5a,8a-peroxid)
Deriv: Acetyl-24~-ethylcholestan-3~-ol, mp
C2s H44 0 3 (428.63) 128-138 DC, [ana + 15 (CHCI3, c 1.00), from 24~
ethylcholestan-3~-ol with Ac 2 0-pyridine
MS, m/z 458 (M+), 398, 276, 257, 230, 215
Me StL: Pseudevernia furfuracea (L.) Zopf
Lit: Wojciechowski et al. 1973
24~ -Ethylcholest -7-en-3 ~-ol
C29HSOO (414.69)
HO
Crystals (n-hexane), mp 183-184 DC, [a]D - 23.9

(CHCI 3 )
IR (KBr): 975, 1050, 1380, 3420, 3540cm-1
IH-NMR (60MHz,CDCU: 0.81-1.04 (6x-Me),
3.96 (1H,m,H-3), 5.15-5.22 (2H,m,H-22,H-23),
HO
6.35 (2H,q,J=8.4Hz,H-6,H-7)
MS, m/z 428 (M+,4%), 410 (5),397 (21), 396 (57), Crystals, mp 144-147 DC, [anD + 9 (CHCI3, c 1.0)
364 (10), 363 (26),271 (7),253 (12),251 (8), 161 Deriv: Acetyl- 24~-ethylcholest -7 -en -3~-ol, mp
(9),259 (14),157 (12),152 (16), 149 (9),147 (10), 156-163 DC, [ana + 7 (CHCI3 , c 1.0)
145 (14), 121 (14), 119 (20), 109 (24), 107 (24), MS, m/z 456 (M+), 396, 315, 273, 255, 229, 213,
105 (19),95 (26),93 (31),91 (26),83 (29),81 (57), from 24~-ethylcholest-7-en-3~-ol with AczO~py
79 (28), 77 (17),69 (69),67 (44), 57 (28), 55 (100), ridine
53 (17), 43 (71) StL: Pseudevernia furfuracea (L.) Zopf
StL: Dactylina arctica (Hook.) NyL, Peltigera Lit: Wojciechowski et aL 1973
aphthosa (L.) Willd., Usnea florida (L.) Wigg.
TLC: A: 56, B: 66, B': 66, C: 43, E: 38, G: 59
Pecosterol
Lit: Takahashi et al. 1972b; Arditti et aL 1972;
Castedo et aL 1987
24~ -Ethylcholestan-3~-ol Me
Cz9 H sz O (416.71)
HO
3.20 Terpenoids 393
Plates (hydrate with 0.5 H 20), mp 126-l30C,

[an4 + 44.9, crystals, mp 161-163C, [am + 42 Me
(CHCIJ
IR (CHCI3 ): 890,1640, 3600cm-1
lH-NMR (CDCI3 ): 0.61 (3H,s,Me-19), 0.95 (3H,s,
Me-18), 1.01 (6H,d,J=7Hz,Me-26,Me-27), 3.60 HO
(IH,m,H-3), 4.65 (2H,m,=CH 2-28)
Deriv: Acetylfecosterol, mp l36-l38C, [aW + Crystals (acetone), mp 148-151C, [anD - 1.0
34.7 (CHCI 3), mp 159-161C, [anD (CHCU, (CHCI 3 )
from fecosterol with Ac 20-pyridine MS, m/z 378, 363, 253, 237, 210, 195, 183, 157,
MS, m/z 440 (M+,100%), 380, 365, 356, 341, 313 143
StL: Lobaria pulmonaria (L.) Hoffm. Deriv: Acetylfungisterol, mp lSI-162C, [anD-
Lit: Barton et al. 1972; Safe et al. 1975 4 (CHCI3 ), from fungisterol with Ac2 0-pyridine
StL: Pseudevernia furfuracea (L.) Zopf
Fremontol Lit: C.F. Culberson 1969; Wojciechowski et al.
1973; Solberg 1987
Lichesterol
C2s H 44 0 (396.63)
HO Me
Faint yellow crystals
IR (KBr): 710, 760, 820, 857, 930, 965, 1040, 1070,
1150, 1295, l380, 1460, 1650, 2870, 2960, 3400,
3500cm-1 HO
MS, m/z 428 (M+,7%), 413 (4),411 (5),410 (9),
397 (11), 396 (31), 395 (6),394 (10),392 (4), 385 Plates (Et2 0-MeOH), mp 114-115C, [am -
(5),378 (5), 377 (7), 376 (5),363 (21),287 (4),271 26.6 (CHCI 3, c 0.3), mp l32-l34C, [a]D - 34
(8),269 (8),255 (8),253 (19),251 (28),239 (11), (CHC}J
229 (7),215 (9), 211 (l3), 197 (l3) UV (EtOH): end absorption 210nm (3.69)
StL: Bryoria fremontii (Tuck.) Brodo et D. IR (KBr): 805,965, 3400cm-1
Hawksw. lH-NMR (l00MHz,CDCI3): 0.67 (3H,s,Me-18)
Lit: Solberg 1975a 0.81,0.83 (2x3H,2xd,J=7Hz,Me-26,Me-27), 0.91
(3H,d,J=7Hz,Me-28), 1.02 (3H,d,J=7Hz,Me-21),
Fungisterol 1.19 (3H,s,Me-19), 2.28 (IH,m,H-4~), 2.36 (lH,
m,H-4a), 2.52 (2H,m,-CH 2-7), 3.55 (lH,m,H-
C2s H 4S O (400.66) 3), 5.43,(IH,m,H-6), 5.20 (2H,m,H-22,H-23)
MS, m/z 396 (M+,67%), 363 (100), 337 (8), 271
(25),253 (23),217 (11), 211 (12)
Derrv: Acetyllichesterol, plates (Et 20-MeOH),
mp 125-126C, [am - 51.4 (CHCI3, c 0.3), from
lichesterol with Ac 20-pyridine
StL: Xanthoria parietina (1.) Th.Fr. IH-NMR (60MHz,CDCIJ: 3.80 (3H,s,-OMe),

Lit: Lenton et al. 1973b; Anastasia and Fiecchi 5.23 (4H,m,H-6,H-7,H-22,H-23)
1981 StL: Ophioparma ventosa (1.) Norm.
Lit: Bruun and Motzfeldt 1975
241; -Methylcholestan -3 ~-ol
Poriferasterol
C2s H saO (402.68)
Me
Me
Me
HO
HO
Crystals, mp 141-146C, [an + 16.5 (CHCI3, c
Crystals, mp 155-156 C, raW - 50 (CHCI3, C 2.0)
1.0)
MS, m/z 412 (M+), 394, 369, 351, 300, 271, 255,
Deriv: Acetyl-241;-methylcholestan-3~-ol, mp
213
143-147C, [am + 7.5 (CHCI3, c 1.0), from 241;-
Deriv: Acetylporiferasterol, plates (Et 2 0-
methylcholestan-3~-ol with Acp-pyridine
MeOH), mp 146-147C, [aHf - 53 (CHCI3, c 1.0),
MS, m/z 444 (M+), 384, 276, 257, 230, 215
from poriferasterol with Ac2 0-pyridine
StL: Pseudevernia furfuracea (1.) Zopf
IH-NMR (I00MHz,CDCI3 ): 0.70 (3H,s,Me-18),
Lit: Wojciechowski et al. 1973
0.85 (6H,d,J=6Hz,Me-26,Me-27), 0.82 (3H,t,J=
6Hz,Me-29), 1.02 (3H,s,Me-19), 1.03 (3H,d,J=
Sa,8a-Peroxyergosteryl divaricatinate 6Hz,Me-21), 2.01 (3H,s,-OCOMe), 2.28 (IH,m,
(Divaricatinsaure-5a,8a- H-4~), 2.35 (IH,m,H-4a), 4.58 (IH,m,H-3),
peroxyergosterylester) 5.09 (2H,m,H-22,H-23), 5.35 (IH,m,H-6)
C39Hs606 (620.84)
Lit: Lenton et al. 1973a
Me ~-Sitosterol
C29HSOO (414.68)
MeonOH Me
~ 'CO-O Me
Me
Crystals (acetone), mp 171-172 C, [a]D + 1

HO
(CHCI3, C 1.0)
UV (EtOH): 264 (4.16), 302nm (3.77) Prismatic needles (CH 2CI2 -MeOH), mp 140-
IR (KBr): 1643, 3000-3500cm-1 141C, [a]D - 35 (CHC13, c LO)
3.20 Terpenoids 395
IR (KBr): 820, 850, 900, 980, 1040, 1080, 1130, Stigmast-7-en-3~-ol (Schottenol)
1150, 1210, 1250, 1360, 1400, 1470, 1670, 2870-
3000, 3100, 3350 cm-l Cz9HSOO (414.69)
MS, m/z 396, 381, 351, 288, 282, 275, 255, 228,
213, 173, 159, 147
Deriv: Acetyl-~-sitosterol, mp 134C, [al D - 41.5
(CHC13, c 1.0), from ~-sitosterol with Acp-pyri-
dine
StL: Cetrariella delisei (Bory ex Schaer.) Karnef.,
Lecanora dispersa (Pers.) Sommerf.
MC: Fig. 65C,D
Lit: C.F. Culberson 1969; Solberg 1987 Crystals (MeOH), mp 151-151.5C, [al D + 9.1
(CHCI3, c 0.95)
StL: Collema cf. polycarpon Hoffm.
Stigmasta-3,5-dien-7-one
Lit: Huneck and Schmidt 1995
(Stigmasta-3,5-dien-7-on)
C29 H 46 0 (410.66)
Stigmast-4-en-3-one (Stigmast-4-en-3-on)
C29 H 4S O (412.67)
Crystals, mp 117-118C, [al D - 293.5 (CHCI 3, c

0.22) 0
StL: Umbilicaria cylindrica (1.) Del. ex Duby Needles (EtzO-MeOH), mp 95-96.5C, [al D +
Lit: Rowe 1965; Huneck et al. 1995b 81.3 (CHC1 3 )
MS, m/z 412 (M+), 300, 288, 271, 229, 159, 135,
Stigmasta-3,5,22-trien-7 -one 124,107,95,69,55,43
(Stigmasta-3,5,22-trien-7-on) Deriv: Oxime of stigmast-4-en-3-one, mp 175- '
176C (EtOAc), from stigmast-4-en-3-one with
Cz9 H 44 0 (408.64) NH 20H
StL: Cladonia furcata (1.) Hoffm.
Lit: Allemand 1988
Stigmasterol
Cz9 H 4S O ,(412.59)
3

3R,3'R-Form: red plates (pyridine-HzO), mp

Me 222-223C
UV (CHC13): 492nm
MS, m/z 596 (M+,41 %), 594 (2), 504 (7),490 (2),
133 (14), 109 (8),91 (19), 83 (100),69 (15)
CD: LlE385 - 6.2, LlE324 + 24.0
HO
StL: Parmelia omphalodes (1.) Ach.
Plates (CHC13-EtOH), mp 168-170C, [aW - 57 Lit: Czeczuga 1988
(CHC13)
MS, m/z 396,380,365,255, 157, 143
Canthaxanthin
Deriv: Acetylstigmasterol, mp 139-145C, [al D
- 55 (CHC13) C4oH5202 (564.82)
StL: Lobaria pulmonaria (1.) Hoffm., Usnea
articulata (1.) Hoffm.
Lit: Solberg 1987; Ali 1992
3.20.7
Carotenoids
Yellow prisms (benzene-MeOH), mp 218C
Antheraxanthin UV (CHCU: 462nm
lH-NMR (100MHz,CDC13): 1.19 (12H,s,Me-16,
Me-17,Me-16',Me-17'), 1.86 (6H,s,Me-18,Me-
OH 18'),1.96 (12H,s,Me-19,Me-20,Me-19',Me-20')
StL: Ophioparma ventosa (1.) Norm.
HO
Lit: Czygan 1976
Pale yellow leaflets (MeOH), mp 206C

a-Carotene (a-Carotin)
UV (CHC13): 460.5, 490.5 nm
MS, m/z 584 (M+,52%), 582 (6), 568 (22), 566 C4o H 56 (536.85)
(38),504 (80), 492 (19), 352 (21),221 (100), 181
(25),133 (31), 109 (30), 91 (57),83 (30), 73 (5),69
(51),59 (4),43 (90)
Lit: Czygan 1976
Deep violet prisms (benzene-MeOH), mp 187-
188C, [am3.5 + 385 (benzene)
Astaxanthin UV (n-hexane): 420, 445, 475nm
lH-NMR (l00MHz,CDC13): 0.84, 0.91,1.04,1.55,
1.73 (4x3H,4xs,4xMe-), 1.97 (l2H,s,4x-Me)
MS, m/z 536 (M+,100%), 480 (2),444 (11), 430
(2)'
ORD (dioxane): [l345 0, [b16 - 10700, [l296 -
10700, [lz6o + 15280, [l227 - 37000, [l217 -
o 13400
3.20 Terpenoids 397
StL: Ophioparma ventosa (1.) Norm. (12H,s,Me-19,Me-20,Me-19' ,Me-20'), 1.45

Lit: Czygan 1976 (2H,-CH z-2), 1.60 (2H,-CHz-3), 2.11 (2H,
-CHz-3'), 2.02 (2H,-CH z-4), 2.11 (2H,-CH z-4'),
5.11 (1H,=CH-2'), 5.95 (lH,=CH-6'), 6.14, 6.17
~-Carotene (~-Carotin)
(2-1H,=CH-10,=CH-1O'), 6.15, 6.24 (2x1H,
C4o H s6 (536.85) =CH-8,=CH-8'), 6.15, 6.49 (2x1H,=CH-7,=CH-
7'),6.24 (2H,=CH-14,=CH-14'), 6.35 (2H,=CH-
12,=CH-12'), 6.60 (2H,=CH-15,=CH-15'), 6.65,
6.63 (2H,=CH-ll,=CH-ll')
StL: Roccella montagnei Bel.
Lit: C.F. Culberson 1969; Czeczuga 1988
Violet prisms (benzene-MeOH), mp 181-184C ~-Cryptoxanthin

UV (n-pentane): 274 (4.39), 340 (4.17), S 425
(5.00),448 (5.13), 476nm (5.08)
lH-NMR: 1.03 (12H,s,Me-16,Me-17,Me-16',
Me-17'), 1.4 5 (4H,-CH z-2,-CH z-2'), 1.60 (4H,-
CH z-3,-CH z-3'), 1.72 (6H,s,Me-18,Me-18'), Me
1.98 (l2H,s,Me-19,Me-20,Me-19',Me-20'), 2.02 HO
(4H,-CH z-4,-CH z-4'), 6.14 (6H,=CH-7,=CH-8,
=CH-1 0,=CH-7',=CH-8',=CH-1 0'), 6.24 (2H, Yellow crystals (benzene-EtOH), mp 169C
=CH-14,=CH-14'), 6.34 (2H,=CH-12,=CH-12'), UV (acetone): 429, 453, 478nm
6.63 (2H,=CH-15,=CH-15'), 6.65 (2H,=CH-ll, MS, mlz 552 (M+,79%), 550 (10), 534 (19), 460
=CH-11') (4), 442 (2), 339 (19), 313 (100), 262 (41), 239
MS, m/z 536 (M+,44%), 533 (3),444 (15), 430 (4), (38)
133 (34), 109 (22),91 (45),83 (23),69 (100) StL: Xanthoria elegans (Link) Th.Fr.
StL: Roccella fuciformis (1.) DC. TLC: RF 0.75 (n-hexane with 5% acetone)
Lit: Czeczuga 1988 Lit: Czeczuga 1988
y-Carotene (y-Carotin) Echinenone (Echinenon)
C4o H s6 (536.85) C4o H s4 0 (550.83)
19 20
Me Me
3
20' 19'
Violet prisms (benzene), mp 176.5-178C Dark violet needles (benzene-MeOH), mp 192-

UV (n-pentane): 278, 430, 465, 480 nm 193C
IH-NMR (220MHz,CDC1 3): 1.03 (6H,s,Me-16, UV (CS z): 450,480, 520nm
Me-17), 1.61, 1.69 (2x3H,2xs,Me-16',Me-17'), IH-NMR (l00MHz,CDC13): 1.03, 1.18 (2x6H,
1.72 (3H,s,Me-18), 1.83 (3H,s,Me-18'), 1.97 2xs,Me-16,Me-17,Me-16',Me-17'), 1.69, 1.84
(2x3H,2xs,Me-18,Me-18'), 1.98 (12H,s,Me-19, 247 (17), 234 (20),221 (100),208 (15), 181 (56)
Me-20,Me-19',Me-20') StL: Cetraria ericetorum Opiz
StL: Ophioparma ventosa (1.) Norm. Lit: Czeczuga 1988
Lit: Czygan 1976
Neoxanthin
Lutein
18
Me
.. OH
HO ....~: OH 19
1 5 Me OH
Me M .... C~
e Me "CH'"
16 17
Me 17'
Copper red prisms (MeOH), mp 193C, [am3.5 + 20'
160 (CHCI3)
Yellow crystals (MeOH), mp 143-145, 200C
UV (n-hexane): 420, 447, 477nm
[am7.S + 34 (CHCI3)
IR (CHCI3): 967, 1030, 1362, 1380, 1440, 1572,
UV (EtOH): 415, 438, 467nm
1600,2860, 2920, 2960, 3460, 3615 cm- 1
IR (KBr): 962, 1924cm- 1
lH-NMR (100MHz,CDCI3): 0.84, 0.99,1.07,1.62,
lH-NMR (100MHz,CDCIJ: 0.96, 1.06, 1.14,
1.72, 1.90, 1.96 (24H,7xs,8x-Me)
1.33 (4x3H,4xs,Me-16,Me-17,Me-16',Me-17'),
MS, m/z 568 (M+,23%), 566 (2), 550 (31), 476 (8),
1.13, 1.33 (2X3H,2xs,Me-18,Me-18'), 1.79, 1.91
462 (5),430 (3),392 (29),304 (41),133 (38), 109
(2x3H,2xs,Me-19,Me-19'), 1.94 (6H,s,Me-20,
(28),91 (100),83 (14),73 (1),69 (34), 59 (4),43
Me-20')
(36)
MS, m/z 600 (M+,24%), 598 (1), 582 (21),520 (2),
ORD (dioxane): [<1>]333 - 4930, [<1>]291 - 4930, [<1>]263
508 (5), 352 (13),221 (92), 181 (61), 133 (62), 109
+ 6580, [<1>]234 - 19600, [<1>]222 - 12300
(51),91 (100),83 (55),73 (5),69 (77), 59 (6)
Lit: Czygan 1976
Lit: Czygan 1976
Mutatoxanthin
Taraxanthin, Lutein epoxide (Luteinepoxid)
C4oHs603 (584.88)
.. OH
Me
Red crystals (MeOH), mp 177C (evac. capil- Orange prisms (MeOH), mp 184-185, 192 DC,
lary) [am4 + 225 (benzene)
UV (EtOH): 404, 427, 453 nm UV (acetone): 418, 441, 471 nm
MS, m/z 584 (M+,51 %),582 (7), 566 (4), 504 (48), lH-NMR (400MHz,CDCI3 ): 0.85, 0.98 (2x3H,
492 (12),478 (2),438 (10),412 (7),365 (11),352 2xs,Me-16',Me-17'), 1.10, 1.16 (2-3H,2xs,Me-
(32),325 (8),312 (7),299 (13),287 (22), 274 (10), 16,Me-17), 1.19 (3H,s,Me-18), 1.62 (3H,s,Me-
3.21 Pulvinic Acid Derivatives 399
18'),1.92 (3H,s,Me-19'), 1.94 (3H,s,Me-19); 1.97 IH-NMR: 1.07 (12H,s,Me-16,Me-17,Me-16',

(6H,s,Me-20,Me-20'), 2.40 (lH,d,H-6'), 3.93 Me-17'), 1.47, 1.70 (4H,-CH 2-2,-CH 2-2'), 1.74
(lH,m,H-3'), 5.43 (lH,dd,JI=10Hz,J2=16Hz, (6H,s,Me-18,Me-18'), 1.97 (12H,s,Me-19,Me-
H-7'), 5.56 (lH,H-4'), 5.90 (lH,d,J=15Hz,H-7), 20,Me-19',Me-20'), 2.04, 2.39 (4H,-CH 2-4,-
6.0-6.6 (=CH-) CH 2-4'), 4.00 (4H,-CH z-3,-CH2-3'), 6.11 (4H,
MS, m/z 584 (M+,l %), 568 (1), 566 (9), 548 (7), =CH-7,=CH-8,=CH-7',=CH-8'), 6.14 (2H,=CH-
504 (2),486 (6), 474 (2), 221 (36), 181 (27), 91 10,=CH-IO'), 6.24 (2H,=CH-14,=CH-14'), 6.35
(100) (2H=CH-12,=CH-12'), 6.62 (2H,=CH-15,=CH-
StL: Ophioparma ventosa (1.) Norm. 15'), 6.63 (2H,=CH-11,=CH-11')
Lit: Czygan 1976; Czeczuga 1988 MS, m/z 568 (M+,100%), 566 (7), 476 (34), 462
(3), 133 (53), 109 (37), 91 (76),83 (24), 73 (2),69
(45)
Violaxanthin
ORD (dioxane): [<1>]357 + 3200, [<1>]297 - 32000,
[ L63 + 45500, [<1>]232 - 38400, [<1>]216 + 30800
OH Pleurosticta acetabulum (Neck.) Elix et
Lumbsch
Lit: Czygan 1976; Czeczuga 1980
HO
3.21
All-E-form: red prisms (MeOH), mp 208 DC,
Pulvinic Acid Derivatives
[am3.5 + 35 (CHCI3)
UV (dioxane): 421, 447, 475.5 nm
IH-NMR (IOOMHz,CDCU: 0.95,1.12,1.16,1.89, Calycin
1.92 (30H,5xs,10xMe-) C1SHIOO S (306.26)
MS, m/z 600 (M+,18%), 584 (4), 582 (2),566 (3),
564 (2), 550 (2), 520 (3),508 (5),221 (100), 181
(21), 91 (50)
ORD (dioxane): [<1>]316 - 14300, [<1>]274 - 45200,
[LS6 + 30000, [<1>]240 + 30000, [b3 - 18600
StL: Ophioparma ventosa (1.) Norm., Punctelia
subrudecta (Nyl.) Krog
Orange red crystals (acetic acid), mp 246-247,
Lit: Czygan 1976; Czeczuga 1980
249-249.5 DC
UV (MeOH): 241 (4.30), 253 (4.21), 430nm
Zeaxanthin (4.40)
IR (KBr): 670, 690, 730, 750, 782, 790, 840, 888,
904, 962, 1000, 1010, 1040, 1070, 1092, 1152,
1162, 1190, 1236, 1258, 1278, 1300, 1340, 1380,
OH
1440, 1470, 1580, 1600, 1630, 1694, 1780, 2500,
3000, 3500 cm- I
MS, m/z 306 (M+,100%), 250 (5), 161 (90), 153
(5),145 (20), 133 (10), 118 (65),105 (20), 89 (35)
Yellow plates (MeOH), mp 215.5C, [a] - 44 StL: Pseudocyphellaria aurata (Ach.) Vain.
(CHCU TLC: A: 78, B: 81, B': 79, C: 88, E:40
HPLC: Rr 47 Yellow needles (MeOH), mp 135-136C, [am -

Lit: c.P. Culberson 1969 1.86 (CHCI 3, c 6.48)
UV (MeOH): 204,238,280, 364nm
IR (KBr): 698, 702, 718, 736, 780, 830, 852, 922,
Demethylleprapinic acid
938,970,982,1050,1070,1102,1150,1200,1230,
(Demethylleprapinsaure)
1270, 1302, 1330, 1370, 1442, 1492, 1542, 1604,
CI9 H I4 0 6 (338.30) 1652, 1740,2350,2980,3100, 3350cm-1
MS, m/z 435 (M+), 290, 145
M1IOt 1:) Deriv: Epanorin methyl ether, cream-coloured

crystals (benzene), mp 187-188C, from epan-
orin with CH 2 N z
V1~o~ StL: Lecanora epanora (Ach.) Ach.
TLC: A: 68, B: 52, B': 47, C: 58, G: 83
Yellow prisms (CH 2CI2-MeOH), mp 214-215C HPLC: Rr 36
UV (MeOH): 223 (4.80),266.5 (4.74),269 (4.71), Lit: c.P. Culberson 1969
273 (4.69),365 (4.12)
IR (KBr): 700, 730, 760, 795, 810, 880, 960, 1030,
1040, 1060, 1080, 1110, 1150, 1180, 1260, 1390, 2-Hydroxypulvic acid lactone
1455, 1495, 1605, 1770, 3500cm-1 (2-Hydroxypulvinsaurelacton)
lH-NMR (100 MHz,CDCI3 -DMSO-d6): 3.73 (3H, Cl 8HlOOS (306.26)
s,-OMe), 6.80-8.70 (9H,m,9arom.-H), 12.28
(2H,bs,-OH,-COOH)
MS, m/z 338 (M+,570/0), 320 (75), 294 (43), 175
(100),165 (32), 148 (68), 145 (76), 133 (32), 121
(83), 119 (66), 117 (63), 107 (27)
Deriv: Methylleprapinate, mp 150-152C, from
demethylleprapinic acid with CH 2N 2 in Et 20
StL: Lepraria sp. from the Himalayas Physical data unknown
TLC: RF 0.48 (n-hexane: Et 20: HCOOH = 30: StL: Letharia vulpina (1.) Hue
20:6) Lit: Tabacchi and Tsoupras 1987
Lit: Appa Rao et al. 1984
4-Hydroxyvulpinic acid
Epanorin (4-Hydroxyvulpinsaure)
C2sHzsN06 (435.45) Cl9Hl406 (338.30)

Lit: Tabacchi and Tsoupras 1987
3.21 Pulvinic Acid Derivatives 401
Leprapinic acid (Leprapinsaure) H), 7.39-7.40 (3H,rn,3arom.-H), 7.48 (2H,d,J=

9Hz,2arom.-H), 7.57-7.70 (2H,rn,2arorn.-H)
C2oHl606 (352.33)
StL: Chrysothrix chlorina (Ach.) Laundon
3'
Lit: c.P. Culberson 1969; Knight and Pattenden
4' 1979
5'
Pinastric acid (Pinastrinsaure)
3
CZOHl606 (352.33)
Golden-yellow plates (MeOH), mp 164-165C
UV (MeOH): 206, 274, 374nm 3'
4'
IR (KBr): 1441, 1458, 1499, 1603, 1621, 1686,
5'
1776,3030cm-1
IH-NMR: 7.10-7.52 (7H,m,H-2-H-5,H-3'-H-
5'),8.08 (2H,m,H-2',H-6') 5
MS, mlz 352 (M+,60%), 320 (100),292 (20),264 Orange needles (benzene), rnp 200-203 c
(5),208 (5), 175 (75), 145 (60),119 (25), 117 (20), UV (MeOH): 291 (4.38), 383 nrn (3.89)
91 (54), 89 (45) IR (KBr): 660, 670, 700, 710, 720, 740, 772, 792,
Deriv: Leprapinic acid methyl ether, needles 822, 850, 870, 910, 930, 962, 1022, 1062, 1080,
(MeOH), mp 150-152C, from leprapinic acid 1100, 1150, 1182, 1250, 1274, 1308, 1330, 1370,
with CHzN z in EtzO with a trace of MeOH 1418, 1440, 1460, 1492, 1515, 1596, 1662, 1750,
StL: Chrysothrix chlorina (Ach.) Laundon 2550, 3000, 3050, 3500 crn-1
TLC: A: 71, B: 59, B': 53, C: 78, E: 35 IH-NMR (l00MHz,acetone-d6 ): 7.00 (2H,d,J=
HPLC: RJ 28 8.5Hz,H-3,H-5), 7.41 (5H,s,H-2' -H-6'), 8.09
Lit: C.P. Culberson 1969 (2H,d,J=8.5Hz,H-2,H-6)
MS, m/z 352 (M+,85%), 320 (100), 292 (20), 264
Leprapinic acid methyl ether (40),208 (60), 175 (25), 147 (50), 119 (35), 117
(Leprapinsauremethylether) (20),89 (60)
Deriv: Acetylpinastric acid, yellow needles
C21HlS06 (366.35) (EtOH), mp 171-173C, from pinastric acid
with Ac20-H zS0 4
M&
eOOMe
n
OMe? 0 StL: Vulpicida pinastri (Scop.) J.E. Mattson et
M.J. Lai
TLC: A: 70, B: 57, B': 55, C: 78, E: 22
a a HPLC: RJ 29
Needles (MeOH), mp 150-152C
UV (MeOH): S 229 (4.27), 261 (4.14), 336nrn
(4.44)
IR (CHCI 3 ): 1435, 1453, 1493, 1603, 1634, 1736,
1773, 2899, 2994 cm-1
IH-NMR (100 MHz,CDCI3 ): 3.76, 3.81, 3.87
(3x3H,3xs,3x-OMe), 6.92 (2H,d,J=9Hz,2arorn.-
Pulvic acid lactone (PulvinsaurelactQn) StL: Pseudocyphellaria crocata (L.) Vain.

Lit: Maass 1970
C1sHlQ04 (290.26)
Pulvinic acid (Pulvinsaure)

C1S H 12 0 5 (308.28)
Yellow needles (AcOH), mp 222-224, 22rC

~olf {)
UV (MeOH): S 236 (4.36), S 249 (4.12), 256
(4.07), 376nm (4.50)
(Jr1o~
IR (KBr): 660, 690, 722, 778, 800, 852, 874, 920, Yellow crystals (EtOH), mp 215-21rc
948, 1150, 1330, 1360, 1448, 1494, 1600, 1650, UV (MeOH): 256 (4.21), 357nm (3.97)
1800cm-1 lH-NMR (100MHz,acetone-d6 ): 7.25-7.52 (3H,
MS, m/z 290 (M+,850/0), 261 (5), 234 (15), 178 m,H-3-H-5), 7.44 (5H,s,H-2' -H-6'), 8.11 (2H,
(10), 145 (100), 117 (26), 89 (94), 77 (8), 63 (25) m,H-2,H-6)
StL: Candelariella vitellina (Ehrh.) MUll.Arg., MS, m/z 308 (M+), 290, 262, 234
Pseudocyphellaria aurata (Ach.) Vain. Deriv: Vulpinic acid, yellow prisms (EtOH), mp
TLC: A: 80, B: 82, B': 82, C: 90, E: 81 148C, from pulvinic acid with an equimolar
HPLC: R, 43 amount of CH1Nz at OC
Lit: C.F. Culberson 1969 StL: Pseudocyphellaria coronata (Ach.) Th.Fr.
TLC: A: 9, B: 36, B': 42, C: 7, E: 10
Pulvinamide (Pulvinamid) HPLC: R, 18
ClsH13N04 (307.28)
~-:r-l n Rhizocarpic acid (Rhizocarpsaure)

C1s H 23 N0 6 (469.46)
CJ lOXN~
D
~t-l
Yellow crystals, mp 220-221 c (dec.)
CJlOXN:
"'6
UV (CHCl 3): 276 (4.09), 377 nm (4.06)
IR (KBr): 1670, 1767, 3328, 3360, 3447,
4366cm-1
00Me
lH-NMR (60MHz,acetone-d6 ): 7.10, 7.33 (2H,
-NH 1 ), 7.50, 8.15 (10H,m,10arom.-H)
MS, m/z 307 (M+,80/0), 290 (100), 261 (6), 234
(10),178 (10), 162 (3),145 (80), 131 (3),117 (16), Yellow needles (MeOH), mp 176.5-177.5C,
89 (35), 77 (4), 63 (7), 39 (4) [anD + 112 (CHCl 3 , c 2.80)
Deriv: Pulvinamide methyl ether, creamy crys- UV (MeOH): 283 (4,38), 368nm (3.98)
tals (MeOH), mp 218C, from pulvinamide with IR (KBr): 670, 690, 708, 740, 758, 780, 790, 878,
CH1N1 in acetone in 30 min 910,930,950,978, 1000, 1024, 1080, 1120, 1160,
3.22 Cleavage Products of Depsides and Depsidones 403
1180, 1200, 1240, 1300, 1320, 1442, 1496, 1548, 3.22

1606, 1660, 1730, 1758, 2250, 2650, 3000, 3100, Cleavage Products of Oepsides
3450cm-1 and Oepsidones
IH-NMR (60MHz,CDCI3 ): 3.15 (2H,d,benzyl.-
CH z-), 3.76 (3H,s,-COOMe), 4.90 (IH,m,-N- Atranol,2,6-Dihydroxy-4-
CH=), 6.80-8.90 (15H,m,15arom.-H) methylbenzaldehyde (2,6-Dihydroxy-
MS, m/z 469 (M+,400/0), 290 (100), 264 (15), 234 4-methylbenzaldehyd)
(10), 207 (10), 178 (10), 145 (75), 120 (25), 117 see Section 3.7.1, page 155
(20), 88 (50), 77 (10), 63 (8)
CD (dioxane): Ll + 3.26 (275nm)
Deriv: Rhizocarpic acid methyl ether, pale Atranolmonomethylether, 2-Hydroxy-6-
cream needles (n-hexane), mp 139-140.5 DC, methoxy-4-methylbenzaldehyde
from rhizocarpic acid with CHzN z in EtzO (2-Hydroxy-6-methoxy-4-methylbenzaldehyd)
StL: Rhizocarpon geographicum (1.) DC. C9H lO 0 3 (166.17)
TLC: A: 67, B: 41, B': 41, C: 65, E: 22
HPLC: R[ 34
Vulpinic acid (Vulpinsaure)

C19H1405 (322.30)
~o~lD Crystals, mp 78 DC
React: PD yellow
CJJToo: Lit: Koller and Maass 1935
Yellow prisms (EtOH), mp 148 DC Barbatol, 2,6-Dihydroxy-4-

UV (MeOH): 290 (4.34), 366nm (3.93) hydroxymethylbenzaldehyde
IR (KBr): 690, 735, 780, 788, 830, 850, 890, 908, (2,6-Dihydroxy-4-hydroxymethylbenzaldehyd)
954, 1000, 1065, 1076, 1154, 1180, 1276, 1300,
1315, 1370, 1440, 1462, 1492, 1608, 1670, 1758, CSH S04 (168.14)
2530, 3000, 3080, 3550 cm-1
MS, m/z 322 (M+,500/0), 290 (100), 261 (8), 234
(15),177 (12),145 (90), 117 (20),89 (46), 77 (15),
63 (12) ,
Deriv: Vulpinic acid methyl ether, yellow crys-
tals (MeOH), mp 142-143 DC from vulpinic acid
with CHzNz in EtzO at 20 DC
TLC: A: 71, B; 66, B': 54, C: 76, E: 18 Yellowish brown prisms (H 2 0), mp 186-189 DC
HPLC: R[ 25 React: PD yellow, PeCl3 olive brown
Lit: c.P. Culberson 1969; Weinstock et al. 1979; HPLC: RJ 10
Brassy et al. 1985 Lit: Schopf et al. 1931
Benzyl orsellinate, Benzyl 2,4-dihydroxy-6- OMe

methylbenzoate (Orsellin-
saurebenzylester,2,4-Dihydroxy-6-
~COOH
methylbenzoesaurebenzylester) ~OMe
C1s H I4 0 4 (258.26) Cl
b'
S Plates (cyclohexane-EtOAc), mp 133, 135-
Me 2' 136C
~OO-CH2~ lH-NMR (CDCI 3): 3.83, 3.86 (2x3H,2xs,2x-
2 ' OMe), 6.87 (lH,d,J=9.6Hz,H-5), 7.42 (1H,d,J=
HO 4 OH 5
9.6Hz,H-4)
MS, m/z 216 (M+,860/0), 199 (31), 141 (100)
Needles (cyclohexane), mp 137-138C Lit: Doyle et al. 1963; Jiang 1991
lH-NMR (CDCU: 2.43 (3H,s,Me-8), 5.21 (lH,
bs,HO-4), 5.35 (2H,s,-O-CH z-), 6.20 (2H,s,H- 2-Chloro-3,5-dimethoxyphenol
5),7.37 (5H,m,H-2'-H-5'), 11.67 (lH,s,-HO-2) (2-Chlor-3,5-dimethoxyphenol)
MS, m/z 258 (M+,30/0), 196 (5), 191 (9),150 (30),
122 (ll), 94 (4), 92 (7), 91 (100) CsH9 CI0 3 (188.60)
TLC: RF 0.39 (EtOAc:n-hexane = 15:85)
Lit: Elix and Norfolk 1975b
1]('
OH
3-Chloro-2,6-dihydroxybenzoic acid
(3-Chlor-2,6-dihydroxybenzoesaure) MeO 5 3 OMe
C7HsCI0 4 (188.56)
Crystals, mp 59-61C
lH-NMR (CDCI3 ): 3.77, 3.85 (2x3H,2xs,2x
OH
-OMe), 5.72 (1H,s,-OH), 6.12 (1H,d,J=2Hz,H-
~COOH 4), 6.24 (1H,d,J=2Hz,H-6)
MS, m/z 188 (M+,100%), 159 (21), 145 (37)
~OH Lit: Grove et al. 1952; Jiang 1991
Cl
4-Chloro-3,5-dimethoxyphenol
Pale pink crystals (HzO'), mp 189, 190-193C (4-Chlor-3,5-dimethoxyphenol
lH-NMR (acetone-d6 ): 6.47 (1H,d,J=8.8Hz,H- CsH9 CI0 3 (188.60)
5), 7.41 (lH,d,J=8.8Hz,H-4)
Lit: Doyle et al. 1963; Jiang 1991
3-Chloro-2,6-dimethoxybenzoic acid
(3-Chlor-2,6-dimethoxybenzoesaure)
C9 H9CI0 4 (216.61)
Prisms (cyclohexane-CH 2CI2), mp 132-134C 5-Chlorohaematommic acid, 2,D-dihydroxy-

IH-NMR (CDCI 3 ): 3.85 (6H,s,2x-OMe), 6.12 3-formyl-5-chloro-6-methylbenzoic acid
(2H,s,H-2,H-6) (5-Chlorhaematommsaure,2,4-Dihydroxy-
MS, m/z 188 (M+,1000/0), 159 (22), 154 (14) 3-formyl-5-chlor-6-methylbenzoesaure)
Lit: Grove et al. 1952; Jiang 1991
C9H 7CIO s (230.59)
Me
5-Chlorodivaricatinic acid, 2-Hydroxy-4-
methoxy-5-chloro-6-n-propyl-benzoic acid C [ * ' COOH
(5-Chlordivaricatinsaure, 2-Hydroxy-4- 5 2
methoxy-5-chlor-6-n -propylbenzoesaure) HO 4 3 OH
CHO
Cl1H!3C104 (244.66)
Me Crystals (AcOH), mp 179.5-180.5C (dec.)
React: KOH yellow, PD yellow
CI~'5 2
COOH
Deriv: Methyl 5-chlorohaematommate, mp
155C, from 5-chlorohaematommic acid with
the equivalent amount of CH2 N2 in Etp at OC
MeO 4 OH
Lit: Koller and P6p11934a,b
Plates (MeOH-H 20), mp 135-136C
IR (KBr): 684, 750, 792, 846, 886, 952,1014,1034,
1066, 1114, 1170, 1218, 1244, 1364, 1434, 1460, 3-Chloro-4-0-methylolivetolcarboxylic acid,
1590, 1630,3000, 3150cm-1 2-Hydroxy-3-chloro-4-methoxy-6-n-
MS, mlz 244 (M+,820/0), 228 (83), 227 (61), 226 pentylbenzoic acid (3-Chlor-4-0-
(100), 171 (59), 170 (38), 169 (83), 135 (35) methylolivetolcarbonsaure, 2-Hydroxy-3-
Lit: Huneck et al. 1980a chlor-4-methoxy-6-n -pen tylbenzoesaure)
C!3H17CI04 (272.72)
3-Chloroeverninic acid, 2-Hydroxy-3-
chloro-4-methoxy-6-methylbenzoic acid
(3-Chloreverninsaure, 2-Hydroxy-3-chlor-
4-methoxy-6-methylbenzoesaure)
C9H 9 CI0 4 (216.61) COOH
Me
h COOH
MeO
CI
OH
MeO~OH Needles (CH 2 CI2-n-pentane), mp 140C

CI IH-NMR (CDCI 3 ): 0.90 (3H,bt,Me-5'), 1.30-1.55
Crystals (acetone), mp 230-233C (4H,m,-CH 2-3',-CH 2-4'). 1.75-1.85 (2H,m,-
IH-NMR (CDCIJ: 2.32 (3H,s,-Me), 3.90 (3H, CH2-2'), 2.95 (2H,bt,J=7Hz,-CH 2-1'), 3.95 (3H,
s,-OMe), 6.64 (1H,s,H-5), 3.35 (2H,bs,-OH,- s,-OMe), 6.39 (1H,s,H-5), 12.2 (2H,bs,-OH,
COOH) . -COOH)
MS, m/z 216 (M+,160/0), 198 (100) MS, m/z 272 (M+'l0/0), 228 (17), 172 (100)
Lit: Elix et al. 1988 Lit: Elix et al. 1988
S-Chloro-~-orcinolcarboxylic acid, 2~4- 5-Chlororhizonic acid, 2-Hydroxy-3,6-

Dihydroxy-3,6-dimethyl-S-chlorobenzoic acid dimethyl-4-methoxy-S-chlorobenzoic acid
(S-Chlor-~-orcinolcarbonsaure, 2.4- (5-Chlorrhizonsaure, 2-Hydroxy-3,6-dimethyl-
Dihydroxy-3,6-dimethyl-S-chlorbenzoesaure) 4-methoxy-5-chlorbenzoesaure)
C9 H9 CI0 4 (216.61) ClO H ll CI0 4 (230.69)
9
Me Me
C I # 1 bOOH C I * 1 COOH
5 2 5 2
HO 4 3 OH MeO 4 3 OH
Me ME:'
8
Crystals (EtOH-H 20), mp 167-168 DC (dec.)
Needles (MeOH-HzO), mp 220-221 D(dec.) React: FeCl3 violet
React: NaOCI red Deriv: Methyl 5-chlororhizonate, mp 75-77 DC
13C-NMR (25.05MHz,DMSO-d6 ): C~l: 107.0, C- (MeOH), from 5-chlororhizonic acid with the
2: 159.5, C-3: 110.5, C-4: 154.9, C-5: 114.0, C-6: calculated amount of CH zN 2 at 0 DC
135.3, C-7: 173.0, C-8: 9.2, C-9: 19.2
Cyclopaldic acid, 2-Methoxy-3-methyl-4-
S-Chloroorsellinic acid, 2,4-Dihydroxy-S- hydroxy-S,6-diformylbenzoic acid
chloro-6-methylbenzoic acid (5-Chlor- (Cyc1opaldsaure,2-Methoxy-3-methyl-4-
orsellinsaure, 2,4-Dihydroxy-5-chlor- hydroxy-5,6-diformylbenzoesaure)
6-methylbenzoesaure)
Cll H lO 0 6 (238.19)
CsH7CI0 4 (202.58)
8 CHO
Me
O H C # ' COOH
CI~tOOH 5 2
HO 4 3 oME:'
~ OH
HO 4 3 Me
Needles (benzene-MeOH), mp 182.5-184 DC Crystals (H 2 0), mp 224-225 DC

(dec.) Deriv: Acetylcyc10paldic acid, mp 159 DC
React: NaOCI red , (EtOH-H 2 0), from cyc10paldic acid with Ac2 0-
13C-NMR (25.05 MHz,DMSO-d6 ): C-1: 111.0a, C- H 2 S04
2: 156.2b , C-3: 101.4, C-4: 158.1 b , C-5: 112.4a, C- Lit: Achenbach et al. 1985
6: 137.0, C-7: 171.0, C-8: 18.5; values marked
with a and b may be exchanged
4-0-Demethylglomellin, Lactone of 2,4-
Deriv: Methyl 2,4-dihydroxy-S-chloro-6-meth-
dihydroxy-6-(2' -hydroxy-n-pent-l ' -enyl)-
ylbenzoate, mp 133-134 DC, from 2,4-dihy-
benzoic acid [Lacton von 2,4-Dihydroxy-
droxy-5-chloro-6-methylbenzoic acid with the
6-(2' -hydroxy-n-pent-1' -enyl)-benzoesaure]
calculated amount of CHzN z in EtzO at -10 DC
Lit: Santesson 1970c C12 H I2 0 4 (220.22)
5' Me
Me
sk eOOH
M'O~OM'
eOOH
HO Crystals (EtzO), mp 212C (dec.)

Lit: Asahina and Yanagita 1933a
Prisms (MeOH), mp 144-145C
React: NaOCl red, FeC13 (EtOH) violet 2,4-Dicarboxy-3-hydroxy-S-methoxytoluene
UV (MeOH): 201 (4.04), S 238 (4.43),245 (4.51), (2,4-Dicarboxy-3-hydroxy-5-methoxytoluen)
258 (3.90),280 (3.65), 328nm (3.60)
IR (KBr): 700, 720, 760, 802, 860, 976,1062,1110, CIOH lO 0 6 (226.18)
1148, 1178, 1250, 1390, 1490, 1570, 1620, 1670,
4
3000, 3250 cm- 1 Me
MS, mlz 220 (M-)
Lit: Huneck and Follmann 1973 5 3 eOOH
MeO 4 OH
2,4-Diacetoxy-3,5,6-trimethylbenzoic acid eOOH
(2,4-Diacetoxy-3,5,6-trimethylbenzoesaure)
Crystals, mp 207-208C (dec.)
Cl4Hl606 (280.27) Lit: Asahina and Yanagita 1933a
10
Me
9 *Me
6 1 eaOH
7 2,4-Dicarboxy-3-methoxy-S-hydroxytoluene
5 2 (2,4-Dicarboxy-3-methoxy-5-hydroxytoluen)
AcO 4 3 OAc
CIOH lO 0 6 (226.18)
Me
4
8
Me
2 eOOH
Crystals, mp 151-155C 5 3
lH-NMR (CDClJ: 2.28, 2.35 (2x3H,2xs,2xAc-), HO 4 OMe
1.96, 2.08, 2.35 (3x3H,3xs,3x-Me, 10.36 (IH,s, eOOH
-COOH)
Deriv: Methyl 2,4-diacetoxy-3,5,6-trimethyl-
Plates (benzene), mp 158C (dec.)
benzoate, mp 123-124C, from 2,4-diacetoxy-
React: FeC13 (EtOH) violet
3,5,6-trimethylbenzoic acid with CHzNz
Lit: Asahina and Simosato 1938
Lit: Andres et al. 1967
3,S-Dichloroeverninic acid, 2-Hydroxy-3,S-

2,4-Dicarboxy-3,5-dimethoxytoluene
dichloro-4-methoxy-6-methylbenzoic acid
(2,4-Dicarboxy-3,5-dimethoxytoluen)
(3,5-Dichloreverninsaure, 2-Hydroxy-3,5-
Cll H 12 0 6 (240.21) dichlor-4-methoxy-6-methylbenzoesaure)
Prisms (H 20), mp 129-130C

UV (EtOH): 284nm (3.10)
Me lH-NMR (90MHz,pyridine-ds): 2.57 (3H,s,Me-
8),4.10 (3H,s,-OMe), 12.60 (lH,s,-COOH)
C l * ' COOH 13C-NMR (pyridine-ds): C-1: 125.5, C-2: 152.7,
5 2
CI
MeO 4 3 OH C-3: 115.3, C-4: 152.3, C-5: 119.7, C-6: 132.7,
C-7: 169.7, C-8: 17.92
Lit: Galmarini and Deulofeu 1961; Dornhagen
and Scharf 1985a,b
Needles (benzene-n-hexane), mp 189-190C
(dec.) 3,5-Dichloroolivetolcarboxylic acid,
Lit: Arshad et aL 1971 2,4-Dihydroxy-3,5-dichloro-6-n-pentylbenzoic
acid (3,5-Dichlorolivetolcarbonsaure, 2,4-
2,4-Dichloro-3-hydroxy-5-methoxytoluene Dihydroxy-3,5-dichlor-6-n -pentylbenzoesaure)
(2,4-Dichlor-3-hydroxy-5-methoxytoluen)
C12H14C1204 (293.04)
CsH sCl2 0 2 (207.05)
5'
h
Me
el
MeO~OH CI COOH
el
HO OH
Crystals, mp 67-68 C
lH-NMR (DMSO-d6 ): 2.28 (3H,s,-Me), 3.80
(3H,s,-OMe), 6.65 (1H,s,H-6), 9.75 (lH,s,-OH) Needles (n-hexane), mp 130-131C
Lit: Dornhagen and Scharf 1985a,b React: NaOCI red, FeCl3 (EtOH) blue-violet
IR (KBr): 692, 780, 820, 1088, 1118, 1144, 1210,
3,5-Dichloroisoeverninic acid, 2-Methoxy- 1260, 1322, 1370, 1410, 1464, 1580, 1650, 2950,
3,5-dichloro-4-hydroxy-6-methylbenzoic acid 3250, 3450 cm-1
(3,5-Dichlorisoeverninsaure, 2-Methoxy- lH-NMR (270MHz,CDCI3 ): 0.92 (3H,t,Me-5'),
3,5-dichlor-4-hydroxy-6;"methylbenzoesaure) 1.39 (4H,m,-CH 2-3',-CH2-4'), 1.58 (2H,m,
-CH 2-2'), 3.15 (2H,t,-CHz-1'), 6.50 (3H,bs,2x
C9HsCl20 4 (251.06) -OH,-COOH)
MS, m/z 296 (M+,2%), 294 (7),292 (14),278 (12),
8 276 (29),274 (43),252 (5),250 (14),248 (29),196
Me (16),194 (67), 192 (100)
CI*'
HO
5
4 3
2 lOOH
OMe
Lit:'Huneck et aL 1977a
Cl
2,4-Dichloroorcinol, 2,4-Dic:hloro- ME'

3,5-dihydroxytoluene
(2,4-Dichlororcinol, 2,4-Dichlor- h CHO
3,5-dihydroxytoluen) HO~OH
CHO
C7H 6 ClzOz (193.02)
Crystals (CCl4 ), mp 126-127 DC

UV (EtOH): 261 (4.38), S 272 (4.29), 344nm
(3.81)
IR (KBr): 1630, 1655cm-1
lH-NMR (60MHz,CDClJ: 2.55 (3H,s,Me-8),
6.27 (1H,s,H-4), 10.05, 10.30 (2x1H,2xs,2x
Crystals (benzene), mp 121 DC -CHO), 12.65, 13.55 (2x1H,2xs,2x-OH)
Lit: Nolan and Murphy 1940 MS, m/z 180 (M+,100%), 152 (93), 151 (70), 134
(2), 133 (4), 106 (14)
Lit: Grundmann and Richter 1966; Bruun 1971a
3,5-Dichloroorsellinic acid, 2,4-Dihydroxy-
3,5-dichloro-6-methylbenzoic acid
(3,5-Dichlororsellinsaure, 2,4-Dihydroxy- 2,6-Diformyl-3,5-dihydroxytoluene
3,5-dichlor-6-methylbenzoesaure) (2,6-Diformyl-3,5-dihydroxytoluen)
CSH 6Cl 20 4 (237.03) C9H s04 (180.15)
ME' ME'
C I * 1 COOH OHC~CHO
5 2
HO 4 3 OH HO ~
5 OH
CI
Yellow needles, mp 175-176 DC
Needles (MeOH-HzO), mp 201-202 DC (dec.) React: NaOCl red, PD yellow
React: NaOCl red, FeCl3 violet Lit: Grundmann and Richter 1966
IR (KBr): 685, 760, 810, 842, 900, 1020, 1092,
1145, 1190, 1215, 1250, 1380, 1400, 1410, 1430,
1460, 1550, 1580, 1630,2900, 3520, 3650 cm- 1 2,5-Dihydroxy-4-methoxy-
Deriv: Methyl 3,5-dichloroorsellinate, mp 120- 6-methylbenzaldehyde
121 DC (MeOH-HzO), fr'om 3,5-dichloro- (2,5-Dihydroxy-4-methoxy-6-

orsellinic acid with the calculated amount of methylbenzaldehyd)
CH 2N2 in Et 20 at DC C9 H lO 0 4 (182.17)
Lit: Huneck 1966a
'ME'
2,4-Diformyl-3,5-dihydroxytoluene HO~CHO
(2,4-Diformyl-3,5-dihydroxytoluen)
C9H s04 (180.15)
~ OH
ME'G 4 3
Yellow prisms (EtOH-H 2 0), mp 162-163C Needles (MeOH-Hp), mp 181C

React: FeCl3 bluish green, fading React: FeCl3 violet brown
Deriv: 2,4,5-Trimethoxy-6-methylbenzalde- Lit: Whalley 1949
hyde, prisms, mp 103-104C, from 2,5-
dihydroxy -4-methoxy-6-methylbenzaldehyde
1,3-Dihydroxy-2,4,5-trimethylbenzene
with dimethyl sulphate-K2 C0 3in acetone in 12h
(1,3-Dihydroxy-2,4,5-trimethylbenzen)
Lit: Aghoramurthy and Seshadri 1952
C9H 12 0 2 (152.19)
2,5-Dihydroxy-3-methoxytoluene
(2,5-Dihydroxy-3-methoxytoluen)
MEC'*Me
6
CSHlO03 (154.16) 4 1
HO 3 2 OH
MEC'
~OH MEC'
HO~OMEC' Crystals, mp 152-153C

IH-NMR: 6.22 (1H,s,H-6)
Needles (benzene), mp 128-129C Deriv: 1,3-Diacetoxy-2,4,5-trimethylbenzene,
Lit: Aghoramurthy and Seshadri 1952 mp 74-75C, from 1,3-dihydroxy-2,4,5-tri-
methylbenzene with Ac 20-H 2S04
3,5-Dihydroxy-4-methylbenzoic acid Lit: Kraus 1891; Whalley 1949
(3,5-Dihydroxy-4-methylbenzoesaure)
CSHS04 (168.14) 2,4-Dimethoxycarbonyl-3-methoxy-
5-hydroxytoluene (2,4-Di-
HOrrCOOH
methoxycarbonyl-3-methoxy-
MEC'~ 5-hydroxytoluen)
OH C12 H 14 0 6 (254.23)
4
Crystals, mp 264-265C Me
React. NaOCI red 2 COOMEC'
IH-NMR (acetone-d6 ): 2.16 (3H,s,-Me), 5.35
5 3
(2H,bs,2x-OH), 7.18 (2H,s,H-2,-H-6) HO 4 OMEC'
Lit: Briggs and Whalley 1976; Borchardt and
COOMe
Sinhababu 1981
Rhombic plates (MeOH or n-pentane), mp
2,4-Dihydroxy-3,5,6-trimethylbenzaldehyde 52.2C
(2,4-Dihydroxy-3,5,6-trimethylbenzaldehyd) React: FeCl3 (EtOH) violet-red
Lit: Asahina and Simosato 1938
CIO H 12 0 3 (180.20)
MEC'
2,6-Dimethoxy-3-chloro-4-methylbenzoic acid
MEC'*CHO
(2,6-Dimethoxy-3-chlor-4-methylbenzoesaure)
HOOH ClO H ll CI0 4 (230.64)
MEC'
OMe IH-NMR (CDCI3): 2.25 (6H,s,2x-Me), 3.66, 3.72

h
Me~OMe
COOH
(2x3H,2xs,2x-OMe), 6.53 (2H,s,H-3,H-5)
MS, m/z 166 (M+,57%), 152 (11), 151 (100)
Lit: Jiang 1991
Cl
2,4-Dimethoxy-6-n-heptylbenzoic acid
Crystals (EtOH-H 2 0), mp 157-158 DC (2,4-Dimethoxy-6-n -heptylbenzoesaure)
Deriv: Methyl 2,6-dimethoxy-3-chloro-4-meth-
CI6 H24 0 4 (280.35)
ylbenzoate, mp 71-72 DC, from 2,6-dimethoxy-
3-chloro-4-methylbenzoic acid with CH 2N2
7'
Lit: Koller and P6pl1934a ME'
2,6-Dimethoxy-3,5-dichlorobenzoic acid
(2,6-Dimethoxy-3,5-dichlor-benzoesaure)
C9H sCl2 0 4 (251.06) 1 COOH
OMe
C!~l
5 2
COOH
Plates (cyclohexane), mp 51-52, 66-67 DC
3 OMe IH-NMR (CDCI3 ): 0.85 (3H,t,J=6.9Hz,Me-7'),
C! 1.09-1.54 (10H,m,-CH 2-2' -6'), 2.50 (2H,bt,J=
7.9Hz,-CH2-1'), 3.76, 3.80 (2x3H,2xs,2x-OMe),
Crystals (n-hexane), mp 95-97, 99-100 DC 6.35, 6.40 (2x1H,2xd,J=1.9Hz, H-3,H-5), 8.90
IH-NMR (CDCI3 ): 3.92 (H,s,2x-OMe), 7.46 (lH, (1H,bs,-COOH)
s,H-4), 9.79 (lH,bs,-OH). Lit: Durrani and Tyman 1980; Elix et al. 1994b
MS, m/z 254 (M+,8%), 252 (46), 250 (72), 235
(10),233 (15),218 (19),205 (41), 175 (100) 2,4-Dimethoxy-6-methylbenzaldehyde
Lit: Elix and Portelli 1990; Jiang 1991 (2,4-Dimethoxy-6-methylbenzaldehyd)
ClO H l2 0 3 (180.20)
1,4-Dimethoxy-2,6-dimethylbenzene
(1,4-Dimethoxy-2,6-dimethylbenzen) Me
ClO H l40 2 (166.21) ~CHO

OMe
MeO ~ OMe
M'~M' Needles (EtOAc-n-hexane), mp 64-65 DC
React: PD yellow
IH-NMR (CDCl3 ): 2.57 (3H,s,-Me), 3.84, 3.86
OMe (2x3H,2xs,2x-OMe), 6.31 (2H,s,H-3,H-5),
10.47 (1H,s,-CHO)
Oil Lit: Hoesch 1913; Jiang 1991
412 3 Data ofLichen Substances
2,4-Dimethoxy-3-methoxycarbonyl- 3,S-Dimethoxyphenol
6-methylbenzoic add (2,4-Dimethoxy-3-
CSHlO03 (154.16)
methoxycarbonyl ~6- methylbenzoesaure)
1:
C12H I4 0 6 (254.23)
ME:'
~ OMe
h
MeO
COOH
MeOOMe
Pale yellow oil, bpo.s 139-141 DC, bpzo 185-190 DC
IH-NMR (CDCI3): 3.74 (6H,s,2x-OMe), 5.22
COOMe
(1H,s,-OH),6.03 (3H,s,H-2, H-4, H-6)
Lit: Pratt and Robinson 1924; Jiang 1991
Crystals, mp 124 DC
Lit: Asahina and Tanase 1937 2,4-Dimethoxy-3,S,6-trimethylbenzoic acid
(2,4-Dimethoxy-3,5,6-trimethylbenzoesaure)
2,4-Dimethoxy-6-( 3' -oxo-n-pentyl)- C12H 16 0 4 (224.25)
benzoic acid [2,4-Dimethoxy-6-
(3' -oxo-n-pentyl)-benzoesaure 1 Me
Cl4HlSOS (266.28) Me * 1COOH

5 2
MeO "3 OMe
5'
Me Me
Crystals (CH 2 CI 2 -n-hexane), mp 112-113 DC

IH-NMR (CDCIJ: 2.21, 2.24, 2.32 (3x3H,3xs,3x
COOH -Me), 3.72, 3.83 (2x3H,2xs,2x-OMe)
OMe
MS, m/z 224 (M+,100%)
Crystals, mp 62 DC
2,4-Dimethoxycarbonyl-3-hydroxy-
IH-NMR (CDCIJ: 1.03 (3H,t,J=7.3Hz,Me-5'),
5-methoxytoluene (2,4-
2.42 (2H,q,J=7.3Hz,-CH 2-4'), 2.86 (2H,t,J=
Dimethoxycarbonyl-3-hydroxy-
6.6Hz,-CH 2-2'), 3.00 '(2H,t,J=6.6Hz,-CH2-1'),
5-methoxytoluen)
3.82 (3H,s,MeO-4), 3.90 (3H,s,MeO-2), 6.41
(2H,AB-q,J=2.lHz,H-3,H-5) C12H I4 0 6 (254.23)
4
MS, m/z 266 (M+,18%), 219 (18), 193(26), 192
(22), 191 (100), 165 (28), 163 (11) Me
Lit: Elix and Jayanthi 1986 2 COOMe
5 3
MeO "OH
COOMe
-Plates (MeOH), mp 125 DC Crystals (MeOH-H 20), mp 78 DC

React: FeCl3 (EtOH) violet-red React: PD yellow
Lit: Asahina and Simosato 1938 Lit: Koller and Popl1934a
1,2-Dimethyl-3-hydroxy-5-methoxybenzene Di-O-methyl-3,5-dichloroorsellinic acid, 2,4-

(1,2-Dimethyl-3-hydroxy-5-methoxybenzen) Dimethoxy-3,5-dichloro-6-methylbenzoic acid
(Di-0-methyl-3,5-dichlororsellinsaure, 2,4-
C9 H 12 0 2 (152.19)
Dimethoxy-3,5-dichlor-6-methylbenzoesaure)
Me ClO H lO Clz0 4 (265.09)
hMe
MeO ~ OH Me
C I * ' eOOH
5 2
Prisms (CC14 ), mp 93-94 DC MeO 4 3 OMe
Lit: Bruun 1971b
Cl
3,5-Dimethyl-4-methoxyphenol
Needles (n-hexane), mp 135-136 C D
C9 H 12 0 2 (152.19) Lit: Nolan and Murphy 1940
M e - r r oH
2,4-Di-O-methyldivaric acid,
Meo~ 2,4-Dimethoxy-6-n -propylbenzoic acid
(2,4-Di -0-methyldivarinsaure,
Me
2,4-Dimethoxy-6-n -propylbenzoesaure)
Pale yellow needles, mp 84-86 DC C12H 16 0 4 (224.25)
lH-NMR (CDCI3): 2.22 (6H,s,2x-Me), 3.66 (3H,
s,-OMe), 6.46 (2H,s,H-2,H-6) 3'
Lit: Bruice et al. 1953; Jiang 1991
2~".
Di-O-methylchloroatranol, 2,6-
Dimethoxy-3-chloro-4-methylbenzaldehyde
(Di -0-methylchloratranol, 1,6-Dimethoxy-3-
chlor-4-methylbenzaldehyd)
MeO n4
3
eOOH
2 OMe
ClO H ll CI0 3 (214.64) Crystals, mp 50-51, 64 DC

lH-NMR (CDCIJ: 0.63-1.20 (3H,t,Me-3'), 1.18-
OMe
2.00 (2B,sextet,-CH 2-2'), 3.06-3.46 (2H,t,-CH z-
~eHO 1'), 3.89, 4.00 (2x3H,2xs,2x-OMe), 6.33-6.53
(2H,m,H-3,H-5), 9.10-9.90 (lH,bs,-COOH)
Me~OMe Lit: Asahina and Hirakata 1932; Durrani and
el Tyman 1980
2,4-Di-O-methyl-5-hydroxyorsellinic acid, 2,4- 2,4-Di-O-methylolivetolcarboxylic acid,

Dimethoxy-5-hydroxy-6-methylbenzoesaure 2,4-Dimethoxy-6-n-pentylbenzoic acid
(2,4-Di-0-methyl-S-hydroxyorsellinsaure,2,4- (2,4-Di -0-methylolivetolcarbonsaure,
Dimethoxy-S-hydroxy-6-methylbenzoesaure) 2,4-Dimethoxy-6-n-pentylbenzoesaure)
CIOH120s (212.20) Cl4Hzo04 (252.30)
5'
Me Me
HotteDDH
MeO 4 OMe
Deriv: Methyl 2,4-di-0-methyl-5-hydroxyorsel-
linate, mp 114-115C, from 2,4-di-0-methyl-5- Needles (n-pentane), mp 52-53C
hydroxyorsellinic acid with the equimolar IR (KBr): 836, 940, 1044, 1070, 1120, 1160, 1200,
amount of CH 2 N2 in Et2 0 at OC 1316, 1420, 1464, 1600, 1700, 2900, 2980,
Lit: Asahina and Kusaka 1942 3330cm-1
lH-NMR (CDCl3 ): 0.60-1.06 (3H,t,Me-5'), 1.06-
Di-O-methylolivetol, 1,3-Dimethoxy-5-n- 2.00 (6H,m,-CH2-2' -CH 2-4'), 2.45-3.00 (2H,
pentylbenzene (1,3-Dimethoxy- t,-CHz-l'), 3.80,3.90 (2x3H,2xs,2x-OMe),
5-n-pentylbenzen) 6.26-6.52 (2H,m,H-3,H-5), 11.00-11.20 (1H,
bs,-COOH)
C13 H 20 0 2 (208.29) Deriv: Methyl 2,4-di-0-methylolivetolcarboxy-
late, oil, bps 175C, from 2,4-di-0-methylolive-
5' tolcarboxylic acid with CH 2N2
Me Lit: Durrani and Tyman 1980
2,4-Di-O-methylolivetonic acid, 2,4-

Dimethoxy-6-(2'-oxo-n-heptyl)-benzoic acid
[2,4-Di-0-methylolivetonsaure, 2,4-
MeO OMe Dimethoxy-6-(2' -oxo-n-heptyl)-benzoesaure]
Cl4H1SOS (266.28)
Oil
lH-NMR (200MHz,CDClJ: 1.90 (3H,t,Me-5'), 7'
1.20-1.40 (4H,m,-CH 2-3',-CH2-4'), 1.50-1.70 Me
(2H,m,-CH 2-2'), 2.70 (2H,t,-CH 2-1', 3.80 (6H,
s,2x-OMe), 6.-30-6.45 (3H,m,H-2,H-4,H-6)
MS, m/z 208 (M+,91%), 179 (15), 166 (74), 152
(100), 137 (47), 123 (51), 122 (33), 121 (44),109
(36)
Lit: Asahina and Fuzikawa 1935a; Birch and
Slobbe 1976
Needles (MeOH-HzO or EtzO), mp 93-94C 13C-NMR (CDCI 3 ): C-1: 101.9, C-2: 161.6, C-3:
IR (KBr): 682, 740, 838, 935, 1045, 1072, 1108, 97.1, C-4: 163.6, C-5: 98.4, C-6: 141.0, C-7:
1160, 1192, 1262, 1316, 1340, 1420, 1460, 1568, 158.1, C-1': 101.9, C-2': 157.6, C-3': 32.9, C-4':
1590, 1704,2850,2930,3200, 3430cm-1 30.8, C-5': 26.1, C-6': 22.1, C-7': 13.8, C-2-
lH-NMR (60 MHz, C6D6): 0.90 (3H,t,Me-7'), OMe: 55.0, C-4-0Me: 55.7
1.05-1.90 (6H,-CH z-4' -6'),2.50 (2H,t,-CH z-3'), Lit: Asahina and Nogami 1942; Jones et al. 1976
3.26, 3.43 (2x3H,2xs,2x-OMe), 3.87 (2H,s,-
CH z-1'), 6.23, 6.35 (2x1H,2xd, J=2Hz,H-3,H-5)
2,4-Di-O-methylorsellinic acid, 2,4-Dimethoxy-
Deriv: 2,4-Di-0-methylolivetonic acid oxime,
6-methylbenzoic acid (2,4-Di-0-
mp 120C, from 2,4-di-0-methylolivetonic acid
methylorsellinsaure, 2,4-Dimethoxy-
with NHzOH
6-methylbenzoesaure)
Lit: Asahina and N ogami 1942
CIOH 12 0 4 (196.20)
2,4-Di-O-methylolivetonide, Lactone of 2,4-
dimethoxy-6-(2' -hydroxy-n-hept-1' -enyl)- 8
benzoic acid [2,4-Di-0-methylolivetonid,
~;~}
Lacton der 2,4-Dimethoxy-6-(2' -hydroxy-n-
hept-1' -enyl)-benzoesaure]
Cl6Hzo04 (276.26)
MeO U4 3
COOH
2 OMe
7' Crystals (EtOH or benzene), mp 145-146C

Me (dec.)
6'
5' UV (MeOH): 210, 252, 280nm
4' lH-NMR (CDC13 ): 2.58 (3H,s,Me-8), 3.80, 3.90
(2x3H,2xs,2x-OMe), 6.22-6.50 (2H,m,H-3,H-
5), 7.00-8.40 (2H,bs,-COOH)
o 13C-NMR (29.05MHz,DMSO-d6): C-1: 117.8, C-
2: 157.1, C-3: 96.0, C-4: 160.5, C-5: 106.6, C-6:
136.4, C-7: 168.7, C-8: 19.3, C-2-0Me, C-4
-OMe: 55.2, 55.7
HPLC: Rr 2.43 min
Needles (MeOH), mp 94-95C Lit: Durrani and Tyman 1980
IR (KBr): 700, 730, 740, 762, 810, 830, 848, 868,
984, 1000, 1020, 1058, 1116, 1150, 1162, 1186,
1210, 1230, 1240, 1290, 1310, 1368, 1420, 1460, Divaric acid, 2,4-Dihydroxy-6-n-propylbenzoic
1564, 1595, 1652, 1720,2850, 2940cm-1 acid (Divarinsaure,2,4-Dihydroxy-6-n-
lH-NMR (60MHz,CDCU: 0.96 (3H,t,Me-7'), propylbenzoesaure)
1.15-2.20 (6H,m,-CH,-4'-6'), 2.50(2H,t,J=7Hz, see Section 3.7.1, page 156
-CH z-3'), 3.94, 4.00 (2x3H,2xs,2x-OMe), 6.13
(lH,s,H-1'), 6.35, 6.45 (2x1H, 2xd,J=2Hz,H-
3,H-5)
416 3 Data ofLichen Substances
Divaricatinic acid, 2-Hydroxy-4-methoxy-6-n- Ethyl 3-bromo-5-methylorsellinate, Ethyl 2,4-

propylbenzoic acid (Divaricatinsaure, 2- dihydroxy-3-bromo-5,6-dimethylbenzoate
H ydroxy-4-methoxy-6-n -propylbenzoesaure) (3-Brom-5-methylorsellinsaureethylester, 2,4-
Dihydroxy-3-brom-5,6-
h
C ll H l4 0 4 (210.22)
dimethylbenzoesaureethylester)
3'
M; CllH!3Br04 (289.12)
" COOH
5612 Me
MeO 4 3 OH
Me*,
5 2
COOC 2H5
HO 4 3 OH
Needles (benzene), mp 157C (dec.)
Br
IR (Nujol): 1170, 1215, 1268, 1575-1660, 2500-
2800cm- 1 Crystals (AcOH-HP), mp 67-69C
IH-NMR (200MHz,CDCI3 ): 1.00 (3H,t,Me-3'), Lit: Canonica et al. 1972
1.50-1.80 (2H,m,-CH z-2'), 2.95 (2H,t,-CH 2-1'),
3.85 (3H,s,-OMe), 6.40 (2H,dd,H-3,H-5), 11.54
(2H,bs,~OH,-COOH)
Ethyl 3-chlorodivarate, Ethyl 2,4-dihydroxy-
MS, m/z 210 (M+,90%), 192 (100), 177 (37), 166 3-chloro-6-n-propylbenzoate
(80), 164 (79), 151 (45), 149 (28), 138 (88), 137 (3-Chlordivarinsa ureethylester, 2,4-Dihydroxy-
(62), 135 (93), 121 (32), 108 (42), 107 (44), 91 3-chlor-6-n-propylbenzoesaureethylester)
(30) C12 H 1sCI0 4 (258.69)
Deriv: Methyl divaricatinate, mp 18-20C, from
divaricatinic acid with the calculated amount of
CHzN z at OC
Me
IH-NMR (200MHz,CDCI3 ): 0.94 (3H,t,J=7Hz,
Me-3'), 1.70 (2H,m,-CH z-2'), 2.85 (2H,t,-CH 2-
I'), 3.78 (3H,s,-OMe), 3.91 (3H,s,-COOMe),
6.30 (2H,dd,J=3Hz,H-3,H-5), 11.70 (lH,s,-OH) HO
MS, m/z 224 (M+,68%), 192 (l00), 164 (55), 135 CI
(79), III (30)
Lit: Sonn 1931b; Dyke et al. 1987
React: NaOCI red
Divarinol, 1,3-Dihydroxy-5-n-propylbenzene IH-NMR (CDCI 3 ): 0.90 (3H,bt,Me-3'), 1.25-1.90
(1,3-Dihydroxy-5-n-propylbenzen) (5H,m,-CH 2-2',-O-CH 2 -Me), 2.50-2.80 (2H,m,
see Section 3.7.1, page 156 -CH 2-1'), 4.50 (2H,q,J=7Hz,-O-CH 2-), 6.17
(IH,s,HO-4), 6.57 (lH,s,H-5), 12.77 (IH,s,
HO~2)
Divarinolmonomethylether,3-Methoxy- MS, m/z 258 (M+,16%), 212 (100)
5-n-propylphenol Lit: Elix et al. 1985c
see Section 3.7.1, page 157
Ethyl 3-chlorodivaricatinate, EthyI2-hydroxy- (2H,q,J=7Hz,-O-CH z-), 6.36 (lH,s,H-5), 12.26

3-chloro-4-methoxy-6-n-propylbenzoate (lH,s,-OH)
(3-Chlordivaricatinsaureethylester, MS, m/z 244 (M+,17%), 198 (100)
2-Hydroxy-3-chlor-4-methoxy- Lit: Elix et al. 1988
6-n -pentylbenzoesaureethylester)
CJ3 H I7Cl0 4 (272.72) Ethyl 3-chloro-4-0-methylolivetolcarboxylate,
Ethy12-hydroxy-3-chloro-4-methoxy-6-n-
3' pentylbenzoate (3-Chlor-4-0-
Me methylolivetolcarbonsaureethylester,
2-Hydroxy-3-chlor-4-methoxy-6-n-
pentylbenzoesaureethylester)
ClsHzICI04 (300.77)

IH-NMR (CDClJ: 0.97 (3H,bt,Me-3'), 1.15-2.25
(5H,m,-CH z-2',-O-CH z-Me), 2.96 (2H, bt,
-CHz-l'), 4.00 (3H,s,-OMe), 4.47 (2H,q,J=7Hz,-
O-CH z-), 6.40 (lH,s,H-5), 12.53 (lH,s,-OH)
CI
MS, m/z 272 (M+,13%), 226 (100)
EthyI3-chloroeverninate, Ethyl 2-hydroxy-3- IH-NMR (CDCl3 ): 0.95 (3H,m,Me-5'), 1.30-1.44
chloro-4-methoxy-6-methylbenzoate (4H,m,-CH z-3',-CH z-4'), 1.46 (3H,t,J=7Hz,-O-
(3-Chloreverninsa ureethylester, CH z-Me),1.75-1.85 (2H,m,-CH z-2'), 2.89 (2H,
2-Hydroxy-3-chlor-4-methoxy-6- bt,-CH z-1'), 3.97 (3H,s,-OMe), 4.46 (2H,q,J=
methylbenzoesaureethylester) 7Hz,-O-CH z-), 6.37 (lH,s,H-5), 12.23 (lH,s,
-OH)
Cll H 13 CI0 4 (244.66) MS, mlz 300 (M+,ll %),254 (100)
Me
5fltCOOC 2H5 Ethyl 3-chloroolivetolcarboxylate, Ethyl 2,4-
dihydroxy-3-chloro-6-n-pentylbenzoate
MeO~OH (3-Chlorolivetolcarbonsaureethylester, 2,4-
CI Dihydroxy-3-chlor-6-n-
pentylbenzoesaureethylester)
Crystals (EtP), mp 146C Cl4Hl9Cl04 (286.74)

IH-NMR (CDCl3 ): 1.42 (3H,t,J=7Hz,-O-CH 2 -
Me), 2.55 (3H,s,Me-8), 3.92 (3H,s,-OMe), 4.43
Ethyl S-chloroorsellinate, Ethyl 2,4-

dihydroxy-S-chloro-6-methylbenzoate
(5-Chlororsellinsaureethylester,
2,4-Dihydroxy-5-chlor-6-
methylbenzoesaureethylester)
HO CIO H ll CI0 4 (230.64)
CI
Needles (CHzClz-n-pentane), mp 50-52C

React: NaOCI red
lH-NMR (CDCI 3): 0.91 (3H,bt,Me-5'), 1.0-1.9
(9H,m,-CH z-2' -4',-O-CHz-Me), 2.72-3.00 (2H,
bt,-CHz-1'), 4.41 (2H,q,J=7Hz,-O-CH 2- ) , 6.01
(lH,s,HO-4), 6.31 (lH,s,H-5), 12.51 (lH,s,HO- Needles (n-hexane), mp 128C
2) React: NaOCI red
MS, m/z 286 (M+,230/0), 240 (100) Lit: Fujikawa et al. 1954
Ethyl 3,S-dichloroolivetolcarboxylate, Ethyl
Ethyl 3-chloroorsellinate, Ethyl 2,4- 2,4-dihydroxy-3,S-dichloro-6-n-pentylbenzoate
dihydroxy-3-chloro-6-methylbenzoate (3,5-Dichlorolivetolcarbonsaureethylester,2,4-
(3-Chlororsellinsaureethylester, 2,4- Dihydroxy-3,5-dichlor-6-n-
Dihydroxy-3-chlor-6- pen tylbenzoesa ureeth ylester )
methylbenzoesaureethylester) Cl4 H 1sCIP4 (321.19)
CIO H ll CI0 4 (230.64)
5'
Me
CI
HO
CI
Prisms (EtOH), mp 146-'148C
React: NaOCI red
lH-NMR (CDCI 3 ): 1.34 (3H,t,J=7Hz,-O-CH 2 - Crystals (cyclohexane), mp 73-75C
Me), 2.34 (3H,s,-Me), 4.17 (2H,q,J=Hz,-O- React: NaOCI red
CH 2-), 6.03 (lH,s,HO-4), 6.84 (lH,s,H-5), 12.02 lH-NMR (CDCI 3): 0.92 (3H,bt,Me-5'), 1.30-1.66
(lH,s,HO-2) (9H;-CH 2-2' -4',-O-CH2 -Me), 3.16 (2H,bt,
Lit: Elix et al. 1988 -CH 2-1'), 4.52 (2H,q,J=7Hz,-O-CH z-), 6.60,
12.44 (2x1H,2xs,2x-OH)
MS, mlz 320 (M+,2%), 273 (100) Crystals (EtOH-n-hexane), mp 62-63C

Lit: Elix et al. 1985c IH-NMR (CDCl3 ): 0.89 (3H,t,J=6.7Hz,Me-9'),
1.27-1.60 (17H,m,-CH z-2' -8',-O-CH z-Me),
2.85 (2H,t,J=7.6Hz,-CHz-1'), 4.40 (2H,q,J=
Ethyl 3,5-dichloroorsellinate, Ethyl 2,4-
7.1Hz,-O-CHz-Me), 6.00 (lH,bs,HO-4), 6.23,
dihydroxy-3,5-dichloro-6-methylbenzoate
6.28 (2X1H,2xd,J=2.6Hz,H-3,H-5), 11.85 (lH,s,
(3,5-Dichlororsellinsaureethylester,
HO-2)
2,4-Dihydroxy-3,5-dichlor-6-
MS, m/z 308 (M+, 36%), 196 (100)
ClOH IO Clz0 4 (265.09)
EthyI2,4-dihydroxy-3,5,6-trimethylbenzoate
Me (2,4-Dihydroxy-3,5,6-
trimethylbenzoesa ureethylester )
C [ * 1 COOC2H5
5 2 C12H 16 0 4 (224.25)
HO 4 3 OH
Me*,
C[
Me
COOC 2 H 5
Crystals, mp 160-163C 5 2
React: NaOCI red HO 4 3 OH
Lit: Fujikawa et al. 1954; Smith 1960
Me
EthyI2,4-dihydroxy-6-n-nonylbenzoate (2,4-
Crystals (EtOAc), mp 83-85, 91-92 C (CCl4 )
Dihydroxy-6-n-nonylbenzoesaureethylester)
React: NaOCI red
C18Hz804 (308.40) UV (EtOH): 218 (4.42), 270nm (4.14)
IR (CCI4 ): 1650,3060, 3590cm-1
9' IH-NMR (220MHz,CDCI3 ): 1.39 (3H,t,J=7.1Hz,
Me -O-CHz-Me), 2.10 (6H,s,-Me-8, Me-9), 2.39
(3H,s,Me-IO), 4.37 (2H,q,J=7.1Hz,-CH 2 -Me),
5.47 (lH,s,HO-4), 11.55 (lH,s,HO-2)
!3C-NMR (55.26 MHz,CDCI3 ): C-1: 106.22, C-
2,C-4: 156.46, 159.39, C-3: 107.20, C-5: 114.70,
C-6: 137.35, C-7: 172.04, C-8: 7.98, C-9,C-IO:
11.81, 14.23, -O-CHz-Me: 18.78, -O-.CHz-Me:
I COOCH 2 -Me 61.15
2 MS, m/z 224 (M+,26%), 150 (100)
OH
Lit: Bartlett et al. 1983; Scott et al. 1986;
McIntyre et al. 1989; Elix et al. 1993a
EthyI2,4-dimethoxy-3,5,6-trimethylbenzoate ME:'
(2,4-Dimethoxy-3,5,6-
trimethylbenzoesaureethylester)
Cl4Hzo04 (252.l3)
MeO oME:'
Cl
Me
Me*COOC 2H5
Oil
ME:'O OME:' IH-NMR (CDCI3 ): 0.90 (3H,m,Me-3'), 1.25-1.90
(5H,m,-CH z-2',-0-CH z-Me), 2.50-2.80 (2H,m,
ME:'
-CH z-1'), 4.00 (6H,s,2x-OMe), 4.45 (2H,q,
J=7Hz,-0-CH z-), 6.67 (1H,s,H-5)
Oil MS, m/z 286 (M+,350/0), 225 (100)
IH-NMR (CDCI3 ): 1.40 (3H,t,J=7Hz,-0-CHz- Lit: Elix et al. 1985c
Me), 2.17, 2.18, 2.21 (3x3H,3xs,3x-Me), 3.68,
3.76 (2x3H,2x5,2x-OMe), 4.41 (2H,q,J=7Hz,-
EthyI2,4-di-O-methyl-3-
O-CH z-)
MS, m/z 252 (M+,400/0), 207 (100) chloroolivetolcarboxylate, Ethyl 2,4-
dimethoxy-3-chloro-6-n-pentylbenzoate
(2,4-Di-0-methyl-3-
chlorolivetolcarbonsaureethylester, 2,4-
Ethyl 2,3-dimethylcyclohexan-4,6- Dimethoxy-3-chlor-6-n-pentylbenzoesaureethylester)
dioncarboxylate (2,3-Dimethylcyclohexan-
4,6-dioncarbonsa ureethylester) Cl6H23CI04 (314.79)
Cll H l6 0 4 (212.24)
ME:'
MeO oME:'
Cl
Viscous yellow oil
IR (CHCI3): 1560, 1650, 1720, 1735cm-1
Lit: Canonica et al. 1972' Oil
IH-NMR (CDCI3 ): 0.89 (3H,bt,Me-5'), 1.25-1.33
(4H,m,-CH z-3',-CH2-4'), 1.35 (3H,t,J=7Hz,-0-
Ethyl di-O-methyl-3-chlorodivarate, Ethyl 2,4-
CH 2-Me), 1.50-1.70 (2H,m,-CH 2-2'), 2.85 (2H,
dimethoxy-3-chloro-6-n-propylbenzoate
bt,J=7Hz,-CHz-1'), 3.89, 3.90 (2x3H,2xs,2x-
(Di-0-methyl-3-chlordivarinsaureeth ylester,
OMe), 4.38 (2H,q,J=7Hz,-0-CH z-), 6.56 (1H,s,
2,4-Dimethoxy-3-chlor-6-n-
H-5)
propylbenzoesaureethylester)
MS, m/z 314 (M+,310/0), 225 (100)
Cl4Hl9CI04 (286.74) Lit: Elix et al. 1988
Ethyl 2,4-di-O-methyl-3-chloroorsellinate, Ethyl divaricatinate, Ethyl 2-hydroxy-4-

Ethyl 2,4-dimethoxy-3-chloro-6- methoxy-6-n-propylbenzoate
methylbenzoate (2,4-Di-O-methyl-3- (Divaricatinsaureethylester, 2-Hydroxy-4-
chlororsellinsaureethylester, 2,4-Dimethoxy- methoxy-6-n -propylbenzoesaureethylester)
3-chlor-6-methylbenzoesaureethylester)
C12H 1sCI0 4 (258.69)
*
6-methylbenzoate (Ethyl everninate, Ethyl 2-
Me hydroxy-4-methoxy-6-
1 COOC2H5 methylbenzoesaureethylester)
MeO 3 OMe
Cl
EthyI5-formyl-~-orcinolcarboxylate, Ethyl
2,4-dihydroxy-3,6-dimethyl-5-formylbenzoate
Oil (5-Formyl- ~-orcinolcarbonsaureethylester,
lH-NMR (CDCI3 ): 1.28 (3H,t,J=7Hz,-O-CH 2- 2,4-Dihydroxy-3,6-dimethyl-5-
Me), 2.13 (3H,s,-Me), 3.59 (3H,s,-OMe), 4.08 formylbenzoesaureethylester)
(2H,q,J=7Hz,-O-CH z-), 6.11 (lH,s,H-5)
MS, m/z 258 (M+,390/0), 213 (100) C12HI 40 S (238.23)
Me
Ethyl divarate, EthyI2,4-dihydroxy-6-n- O H C # l COOC2H5
propylbenzoate (Divarinsaureethylester, 2,4- 5 2
Dihydroxy-6-n -propylbenzoesaureethylester) HO 4 3 OH
Me
C12H I6 0 4 (224.25)
Needles (EtOH), mp 137C

React: FeCl3 (EtOH), reddish brown
Lit: Whalley 1949
Ethyl haematommate, Ethyl 2,4-

dihydroxy-3-formyl-6-methylbenzoate
(Haematommsaureethylester, 2,4-
Needles (EtOH-H 20), mp 96-98C Dihydroxy-3-formyl-6-
React: NaOCI red methylbenzoesaureethylester)
Lit: Sonn 1931b; Kato and Hozumi 1972; Dyke et see Section 3.7.1, page 158
al. 1987
EthyIS-hydroxyeverninate, Ethyl Ethyl isoeverninate, EthyI2-methoxy-4-

2,S-dihydroxy-4-methoxy-6-methylbenzoate hydroxy-6-methylbenzoate
(5-Hydroxyeverninsaureethylester, (Isoeverninsaureethylester, 2-Methoxy-4-
2,5-Dihydroxy-4-methoxy-6- hydroxy-6-methylbenzoesaureethylester)
Cll H l4 0 4 (210.22)
CllHl 40 S (226.22)
Me
~COOC2H5
MeO 4 3 OH
Needles (EtzO-n-pentane), mp 76-77C
IH-NMR (lOOMHz, CDCIJ: 1.38 (3H,t,-O-CH 2 -
Flat needles and rectangular prisms (EtOH), mp Me), 2.22 (3H,s,-Me), 3.64 (3H,s,-OMe), 4.51
106-107C (2H,q,-O-CH z-Me), 6.23 (2H,s,H-3,H-5)
React: FeCl3 blue, changing quickly to green and Lit: Cresp et al. 1973
fading
Deriv: Ethyl diacetyl-5-hydroxyeverninate, mp
Ethyl isohaematommate, Ethyl
134-135C, from ethyl 5-hydroxyeverninate
2,4-dihydroxy-S-formyl-6-methylbenzoate
with ACzO-pyridine
(Isohaematommsaureethylester, 2,4-
Dihydroxy-5-formyl-6-
EthyI2-hydroxy-4-methoxy-3,S,6-
Cll H 12 0 s (224.21)
trimethylbenzoate (2-Hydroxy-4-methoxy-
3,5,6-trimethylbenzoesaureethylester)
Me
C!3HlS04 (238.27)
OHC~l COOC2HS
S 2
Me HO 4 OH
M e * , COOC 2 HS
5 2
MeO 4 3 OH Needles (EtOH-HzD), mp 93-94.5C
Me
Lit: pfau 1933
Crystals (EtOAc-n-hexane), mp 51-52C

EthyI5-methyl-isoeverninate, Ethyl 2-
IH-NMR (CDCI 3): 1.42 (3H,t,]=7Hz,-O-CHz-
methoxy-4-hydroxy-5,6-dimethylbenzoate
Me), 2.17, 2.18, 2.44 (3x3H,3xs,3x-Me), 3.69
(5-Methyl-isoeverninsaureethylester, 2-
(3H,s,-OMe), 4.42 (2H,q,]=7Hz,-O-CH z-),
Methoxy-4-hydroxy-5,6-
11.15 (lH,s,-OH)
dimethylbenzoesaureethylester)
MS, m/z 238 (M+,43%), 193 (l00)
Lit: Elix et al. 1993a C12H I6 0 4 (224.25)
Crystals (EtOH-H 20), mp 62-63C

IR (CHCI3 ): 1595, 1720cm-1
Lit: Canonica et al. 1972
Ethyl 3-methylorsellinate, Ethyl ~

Plates (CH 2CI2-n-hexane), mp 111-112C orcinolcarboxylate, Ethyl 2,4-dihydroxy-
lH-NMR (l00MHz,CDCI3): 1.38 (3H,t,-0-CH 2- 3,6-dimethylbenzoate
Me), 2.07, 2.18 (2x3H,2xs,2x-Me), 3.64 (3H,s,- (3-Methylorsellinsaureethylester, ~
OMe), 4.40 (2H,q,-0-CH 2-Me), 6.02 (lH,bs, Orcinokarbonsaureethylester, 2,4-Dihydroxy-
-OH), 6.23 (lH,s,H-3) 3,6-dimethylbenzoesaureethylester)
Lit: Cresp et al. 1973
Cll H 14 0 4 (210.22)
EthyI2-methoxy-4-hydroxy-5-formyl-6-
Me
methylbenzoate (2-Methoxy-4-hydroxy -5-
formyl-6-methylbenzoesaureethylester) 5~COOC2H5
C12HI 4 0 S (238.23) HO~OH
Me
Needles, mp 124-126C
UV (MeOH): 217 (4.40), 268 (4.31), 295nm
(3.79)
IR (KBr): 1620, 3450cm-1
Plates (CH 2CI2-n-hexane), mp l39-140C
lH-NMR (100 MHz,CDCI3 ): 1.41 (3H,t,J=7.1Hz,
React: PD yellow
-0-CH2-Me), 2.10, 2.48 (2x3H,2xs,2x-Me),
lH-NMR (lOOMHz,CDCIJ: 1.40 (3H,t,-0-CH 2-
4.39 (2H,q,J=7.1Hz,-0-CH 2-), 5.12 (lH,s,-OH),
Me), 2.51 (3H,s,-Me), 3.89 (3H,s,-OMe), 4.41
6.20 (lH,s,H-5), 12.11 (lH,s,-OH)
(2H,q,-0-CH 2-Me), 6.32 (lH,s,H-3), 10.22 (1H,
MS, m/z 210 (M+,310/0), 164 (97), l36 (100)
s,-CHO), 12.80 (lH,s,-OH)
Lit: Kawahara et al. 1988
Ethyl 5-methylorsellinate, Ethyl 2,4-

Ethy15-methyl-di-O-methylorsellinate, Ethyl
dihydroxy-5,6-dimethylbenzoate (5-Methyl-
2,4-dimethoxy-5,6-dimethylbenzoate
orsellinsaureethylester, 2,4-Dihydroxy-
(5-Methyl-di-0-methylorseHinsaureethylester,
5,6-dimethylbenzoesaureethylester )
2,4-Dimethoxy-5,6-
dimethylbenzoesaureethylester) Cll H l4 0 4 (246.25)
C13 H 1S 0 4 (238.27)
Pale cream platelets (CCI4 ), mp 115-t16C 7'

React: NaOCI red Me
Lit: Canonica et a1. 1972; Bartlett et a1. 1983
Ethyl olivetolcarboxylate, Ethyl 2,4-dihydroxy-

6-n-pentylbenzoate
(Olivetolcarbonsaureethylester, 2,4-Dihydroxy-
6-n -pentylbenzoesa ureethylester )
Cl4Hzo04 (252.30)
Me React: NaOCI red
Lit: Kato and Hozumi 1972; Dyke et a1. 1987
Everninaldehyde, 2-Hydroxy-4-methoxy-6-
methylbenzaldehyde (Everninaldehyd, 2-
4
HO H ydroxy-4-methoxy-6-methylbenzaldehyd)
C9H lO 0 3 (166.17)
Prisms (n-hexane or AcOH-HzO), mp 69C
React: NaOCI red
UV (MeOH): 214 (4.47), 262 (4.14), 301nm LCHO
(3.73)
Lit: Korte and Sieper 1960; Kato and Hozumi MeO~OH
1972; Hase et a1. 1978; Dyke et a1. 1987
Crystals (MeOH-H 2 0), mp 65C
Ethyl orsellinate, EthyI2,4-dihydroxy-6- React: HN0 3 cone. bluish green
methylbenzoate (Orsellinsaureethylester, 2,4- IH-NMR (CDCI3 ): 2.45 (3H,s,-Me), 3.79 (3H,s,-
Dihydroxy-6-methylbenzoesaureethylester) OMe), 6.24 (2H,s,H-3,H-5), 10.18 (IH,s,-CHO),
see Section 3.7.1, page 158 12.60 (1H,s,-OH)
Lit: Hoesch 1913; Robertson and Stephenson
1932; Jiang 1991
Ethyl sphaerophorolcarboxylate, Ethyl 2,4-
dihydroxy-6-n-heptylb~nzoate
(Sphaerophorolcarbonsaureethylester, 2,4-
Dihydroxy-6-n -heptylbenzoesaureethylester)
Cl6Hz404 (280.35)
Everninic acid, 2-Hydroxy-4-methoxy-6- 5'

methylbenzok acid (Everninsaure, 2-Hydroxy-
ME.>
4-methoxy-6-methylbenioesaure)
C9H lO 0 4 (182.17)
b
ME.>
1 COOH
4 . 2
ME.> 0 OH Prisms (MeOH), mp 85 DC
Crystals (EtOH-HlO), mp 174-175 DC (dec.) IR (KBr): 698, 750, 808, 850, 878, 980,1040,1062,
IR (KBr): 696, 736, 800, 842, 890,950,998, 1030, 1144, 1160, 1190, 1235, 1350, 1375, 1430, 1462,
1060, 1120, 1158, 1200, 1215, 1260, 1308, 1360, 1510, 1564, 1616, 163~ 167~ 295~ 3100,
1416, 1460, 1500, 1620,3000 cm-1 3460 cm-l
lH-NMR (270MHz,CDCI3): 2.57 (3H,s,-Me), lH-NMR (CDCI3): 0.98 (3H,t,J=7.2Hz,Me-5'),
6.33 (1H,d,J=2.5Hz,H-3), 6.35 (1H,d,J=2.5Hz, 1.72 (2H,sextet,J=7.2Hz,-CH l -4'), 2.47 (2H,t,
H-5), 11.56 (lH,s,HO-2) J=7.2Hz,-CH l -3'), 3.85 (3H,s,-OMe), 6.17 (1H,
13C-NMR (CDCU: C-1: 105.50, C-2: 165.12, C-3: s,H-1'), 6.30 (lH,d,J=2.3Hz,H-5), 6.45 (lH,s,J=
99.46, C-4: 167.17, C-5: 111.43, C-6: 144.46, C- 2.3Hz,H-3)
7: 174.13, C-8: 24.28, -OMe: 55.72 MS, mlz 234 (M+,1000/0), 191 (33), 177 (37), 164
MS, m/z 182 (M+'430/0), 164 (100), 138 (11), 136 (41), 135 (41)
(61), 109 (13) Lit: Minami 1944; Whitton 1989
Deriv: Methyl everninate, prisms (H 20), mp 67-
68 DC, from everninic acid with the calculated Haematommic acid, 2,4-Dihydroxy-3-formyl-
amount of CH l N 2 in EtlO 6-methylbenzoic acid (Haematommsaure, 2,4-
Lit: Robertson and Stephenson 1932; Dihydroxy-3-formyl-6-methylbenzoesaure)
Aghoramurthy and Seshadri 1952; Nishitoba et
aL 1987 see Section 3.7.1, page 158
Fumaric acid (Fumarsaure) 3-Hydroxydivaricatinic acid, 2,3-Dihydroxy-4-

methoxy-6-n-propylbenzoic acid
see Section 3.6.2, page 144 (3-Hydroxydivaricatinsaure, 2,3-Dihydroxy-4-
methoxy-6-n-propylbenzoesaure)
Glomellin, Lactone of 2-hydroxy-4-methoxy-6- CUH1 4 0 S (226.22)
(2' -hydroxy-n-pent-l' -enyl)-benzoic acid
[Lacton der 2-Hydroxy-6-(2'-hydroxy-n-pent-
l' -enyl)-benzoesaure]
C13 H 14 0 4 (234.24)
Prisms (MeOH), mp 141C

lH-NMR (CDCI3 ): 0.99 (3H,t,J=6.6Hz,Me-5'),
1 eOOH
1.41-1.70 (2H,m,-CH 2-4'), 1.81-2.05 (2H,m,-
CH2-3'), 2.94, 3.21 (2H,AB-q,J=6.9Hz,-CH2-1'),
MeO 3.82 (3H,s,-OMe), 6.29 (lH,d,J=2.2Hz,H-3),
6.37 (1H,d,J=2.2Hz,H-5), 11.15 (1H,s,-OH)
MS, m/z 252 (M+,350/0), 234 (30), 209 (11), 208
(16), 181 (20), 165 (30), 164 (100), 135 (17)
Needles (EtOH-H 20), mp 163-164 C Lit: Whitton 1989
React: NaOCI blue, FeCl3 (EtOH) dark green
Lit: Nakao 1923 2-Hydroxy-4-methoxy-6-(3'-oxo-n-pentyl)-
benzoic acid [2-Hydroxy-4-methoxy-6-(3'-oxo-
5-Hydroxyeverninic acid, 2,5-Dihydroxy-4- n-pentyl)-benzoesaure]
methoxy-6-methylbenzoic acid C13 H I6 0 S (252.26)
(5-Hydroxyeverninsaure,2,5-Dihydroxy-4-
methoxy-6-methylbenzoesaure)
C9HlOOS (198.17)
Me , eOOH
HO~eOOH
MeO ~
4 OH
MeO OH
Prisms (benzene), mp 119-120C

Stout rectangular prisms or prismatic needles React: FeCl3 (EtOH) violet
(benzene-n-hexane), mp 172-173C (dec.) UV (MeOH): 222 (4.18),250 (3.78), 278 (4.21),
Lit: Aghoramurthy and Seshadri 1952 300 (4.06), 335nm (4.01)
IR (KBr): 680, 720, 810, 826, 870, 970,1023,1043,
2-Hydroxy-4-methoxy-6-(2' -oxo-n-pentyl)- 1140, 1176, 1200, 1236, 1310, 1410, 1450, 1476,
benzoic acid [2-Hydroxy-4-methoxy-6- 1580, 1610, 1627, 1700, 3440cm-1
(2' -oxo-n-pentyl)-benzoesaure] lH-NMR (60MHz,CDCU: 1.22 (3H,t,Me-5'),
2.28 (2H,t,-CH 2-2'), 2.30 (2H,t,-CH z-1'), 2.83
C13H I6 0 S (252.26) (2H,q,-CH 2-4'), 3.83 (3H,s,-OMe), 6.28, 6.46
(2x1H,2xd,J=2.4Hz,H-3,H-5)
Lit: Huneck et al. 1971; Elix and Jayanthi 1986
5- Hydroxy-~-orcinolcarboxylic acid, 2,4,5-

Trihydroxy-3,6-dimethylbenzoic acid
(5-Hydroxy-~-orcinolcarbonsaure, 2,4,5-
Trihydroxy-3,6-dimethylbenzoesaure)
C9HlOOS (198.17)
Me Crystals (benzene), mp 93C; hydrate, mp 60C

Deriv: Methyl iso-divaricatinate, mp 121C
H O * ' eOOH
~ 2 (MeOH), from iso-divaricatinic acid with the
HO 3 OH calculated amount of CH2N2 in Et2 0 at OC
Me Lit: Asahina and Hirakata 1932
Crystals (Et2 0-benzene), mp 190C Iso-eveminic acid, 2-Methoxy-4-hydroxy-6-

React: KOH red-violet methylbenzoic acid (Iso-everninsaure, 2-
Deriv: Methyl 2,4,5-trihydroxy-3,6-dimethyl- Methoxy-4-hydroxy-6-methylbenzoesaure)
benzoate, mp 151-152C (benzene), from 2,4,5-
C9 H lO0 4 (182.17)
trihydroxy-3,6-dimethylbenzoic acid with the
calculated amount of CH 2N2 in Et20 at OC Me
~eOOH
2-Hydroxy-3,5,6-trimethyl-4-methoxybenzoic HO 4 OMe
acid (2-Hydroxy-3,5,6-trimethyl-4-
methoxybenzoesaure) Plates (acetone-H 20), mp 175C (dec.)
Cll H 140 4 (210.22)
Deriv: Methyl iso-everninate, mp 114C (ben-
zene), from iso-everninic acid with the calcu-
Me lated amount of CH 2N2 in Et 20 at OC
M e * , eOOH Lit: Robertson and Stephenson 1932; Koller and
5 2 Pfeiffer 1933
Mea 4 3 OH
Me
Iso-haematommic acid, 2,4-Dihydroxy-5-
formyl-6-methylbenzoic acid
Crystals (CH 2 CI2-n-pentane), mp 144-145C (Iso-haematommsaure, 2,4-Dihydroxy-5-
IH-NMR (CDCI3 ): 2.19, 2.20, 2.53 (3x3H,3xs,3x formyl-6-methylbenzoesaure)
-Me), 3.72 (3H,s,-OMe), 11.13 (lH,s,-OH)
MS, miz 210 (M+,54%), 164 (100) C9HsOs (196.15)
Lit: Elix et al. 1993a Me
OHe~COOH
Iso-divaricatinic acid, 2-Methoxy-4-hydroxy-6- 5 2
HO 4 OH
n-propylbenzoic acid (Iso-clivaricatinsaure, 2-
Methoxy-4-hydroxy-6-n -propylbenzoesaure) Needles (EtOH-H 20), mp 224-225C
Cll H 140 4 (210.22) Lit: pfau 1933
1
Me
Iso-rhizonic acid, 2-Methoxy-3,6-dimethyl-4-
hydroxybenzoic acid (Iso-rhizoninsaure, 2-
eOOH
Methoxy-3,6-dimethyl-4-hydroxybenzoesaure)
HO 4 OMe ClOH 12 0 4 (196.20)
Me Needles (cyclohexane-EtOAc), mp 128-129C
h COOH lH-NMR (acetone-d6 ): 3.97 (3H,s,-OMe), 6.81

(1H,d,J=9Hz,H-5), 7.56 (lH,d,J=9Hz,H-4)
HO-OMe MS, m/z 202 (M+,17%), 186 (29), 184 (97), 143
Me (33), 141 (100)
Lit: Jiang 1991
Crystals (benzene), mp 154C (dec.)

2-Methoxy-3,6-dimethyl-4-
Deriv: Methyl iso-rhizonate, mp 146C (ben-
hydroxybenzaldehyde (2-Methoxy-3,6-
zene or EtOH), from iso-rhizonic acid with the
dimethyl-4-hydroxybenzaldehyd)
calculated amount of CH2N2 in Et2 0 at OC
Lit: Asahina and Fuzikawa 1932b CIO H 120 3 (180.07)
*
Lobaritonic acid, 2-Hydroxy-4-methoxy-6- 9
(1' -oxo-n-pentyl)-benzoic acid Me 7
[Lobaritonsaure,2-Hydroxy-4-methoxy-6- 5 6 1 CHO
(1' -oxo-n-pentyl)-benzoesaure]
HO 4 3 2 OMe
C13HI 60 S (252.26)
Me
8
Me
Crystals, mp lSI-153C
React: PD yellow
UV (EtOH): 232 (4.11), 284nm (4.15)
IR (KBr): 1660, 3100cm-1
MeO lH-NMR (100MHz,CDCq: 2.18, 2.54 (2x3H,
2xs,2x-Me), 3.83 (3H,s,-OMe), 6.52 (1H,s,H-5),
6.97 (lH,bs,-OH), 10.35 (lH,s,-CHO)
Crystals (benzene), mp 120C 13C-NMR (99.6MHz,CDCI3 ): C-l: 121.01, C-2:
React: FeCl3 (EtOH) violet 165.30, C-3: 115.41, C-4: 159.93, C-5: 114.57, C-
Lit: Asahina and Yasue 1936 6: 141.39, C-7: 191.48, C-2-0Me: 63.10
Lit: Kawahara et al. 1988
2-Methoxy-3-chloro-6-hydroxybenzoic acid
(2-Methoxy-3-chlor-6-hydroxybenzoesaure) 2-Methoxy-4-hydroxy-5-formyl-6-
methylbenzoic acid (2-Methoxy-4-hydroxy-5-
CsH7 CI0 4 (202.58) formyl-6- methylbenzoesaure)
CIOHIOOS (210.18)
OH
~COOH
~OMe
CI
Me 3-Methoxy-4,5,6-trimethylphenol
OHC~COOH ClOH 140 2 (166.21)
HO ~
4 3 OMe
Me
Me~Me
Needles (MeOH-H 2 0), mp 163-164C
React: FeCl3 (EtOH) red, PD yellow MeO ~
3 OH
Deriv: Methyl 2-methoxy-4-hydroxy-5-formyl-
6-methylbenzoate, needles, mp 135C
(EtOH), from 2-methoxy-4-hydroxy-5-formyl- Needles (CCI4 ), mp 122-122.5 C
6-methylbenzoic acid with the calculated Lit: Bruun 1971b
amount of CH2N2 in EtzO at OC
Methyl 3-chloro-di-O-methylorsellinate,
3-Methoxy-2,4,5-trimethylphenol MethyI2,4-dimethoxy-3-chloro-6-methyl-
benzoate (3-Chlor-di-O-
ClO H 140 2 (166.21) methylorsellinsauremethylester,
2,4-Dimethoxy-3-chlor-6-
methylbenzoesauremethylester)
Me*Me Cll H 13 Cl0 4 (244.66)
4 1
*
MeO 3 2 OH
Me
Me
5 6 1 COOMe
Faintly yellow plates in clusters (n-hexane), mp MeO 3 OMe

83-84C CI
Lit: Bruun 1971b
Stout rods (CH 2CI 2-n-pentane), mp 57.5-58C
3-Methoxy-2,5,6-trimethylphenol lH-NMR (80MHz,CDCI3): 2.31 (3H,s,-Me), 3.89,
ClOH 1P2 (166.21) 3.90, 3.91 (3x3H,3xs,2x-OMe,-COOMe), 6.55
(1H,s,H-5)
MS, mlz 246, 244 (M+)
Me Lit: Birkbeck et al. 1990
h Me
MeO~OH Methyl3-chloroeverninate, MethyI2-hydroxy-

3-chloro-4-methoxy-6-methylbenzoate
Me
(3-Chloreverninsauremethylester,
2-HydFoxy-3-chlor-4-methoxy-6-
Crystals (n-hexane), mp 70-71 C methylbenzoesauremethylester)
Lit: Bruun 1971 b C1Q H ll CI0 4 (230.64)
Me 8
Me
5?i;COOMe
CI~l:ooMe
MeOOH
HO ~ OMe
CI
Needles (EtOAc-n-hexane), mp 117C

Needles (CH 2 CI 2-n-hexane), mp 169-170C UV (EtOH): 203 (4.51), 245 (3.69), 288nm (3.49)
lH-NMR (80MHz,CDCI3 ): 2.55 (3H,s,-Me), 3.94, lH-NMR (CDCU: 2.29 (3H,s,-Me), 3.73 (3H,s,
3.96 (2x3H,2xs,2x-OMe), 6.35 (lH,s,H-5), 12.20 -OMe), 3.88 (3H,s,-COOMe), 6.22 (lH,s,-OH),
(lH,s,-OH) 6.44 (IH,s,H-3)
MS, m/z 232, 230 (M+) !3C-NMR (CDCI3 ): C-l, C-5, C-6: 112.54, 117.39,
Lit: Birkbeck et al. 1990 134.89, C-2,C-4: 153.41, 146.16, C-3: 97.54, C-7:
168.34, C-8: 17.47, -OMe, -COOMe: 52.42, 56.00
Methyl 5-chlorohaematommate, Methyl 2,4- Lit: Dornhagen and Scharf 1985a,b
dihydroxy-3-formyl-5-chloro-6-
methylbenzoate Methyl 3-chloroorsellinate, Methyl 2,4-
(5-Chlorhaematommsauremethylester, 2,4- dihydroxy-3-chloro-6-methylbenzoate
Dihydroxy-3-formyl-5-chlor-6-methyl- (3-Chlororsellinsauremethylester,
benzoesauremethylester) 2,4-Dihydroxy-3-chlor-6-
ClOH9CIO s (232.61) methylbenzoesauremethylester)
C9H 9CI0 4 (216.61)
Me
C I * 1 COOMe Me
5 2
5?i;cooMe
HO 4 3 OH
CHO MeOOMe
CI
Crystals (EtOH), mp 90C
React: NaOC 1 red, PD yellow Crystals (benzene), mp 133-134C
Lit: Koller and P6pl1934a IN-NMR (l00MHz,acetone-d6 ): 2.47 (3H,s,
-Me), 3.96 (3H,s,-COOMe), 6.48 (lH,bs,H-5),
12.20 (lH,s,-OH)
MethyI5-chloro-iso-everninate, Methyl 2-
MS, mlz 216 (M+)
methoxy-4-hydroxy-5-chloro-6-
Lit: Evans 1987
methylbenzoate (5-Chlor-iso-
everninsauremethylester, 2-Methoxy-4-
hydroxy-5-chlorbenzoesauremethylester) Methyl 5-chloroorsellinate, Methyl 2,4-
ClO H ll CI0 4 (230.64) dihydroxy-5-chloro-6-methylbenzoate
(5-Chlororsellinsauremethylester, 2,4-
Dihydroxy-5-chlor-6-methylbenzoesaure-
methylester)
8
Me
Me C I * l tOOMe
5 2
CI~COOMe HO 4 3 OMe
HO ~
4 3 OH
Cl
Needles (CH 2 C12 -n-hexane), mp 80-81 C

Crystals (benzene), mp 133-134C IH-NMR (CDCI3 ): 2.30 (3H,s,-Me), 3.87 (3H,s,-
React: NaOCI red OMe), 3.90 (3H,s,-COOMe), 6.23 (lH,s,-OH)
IH-NMR (100MHz,acetone-d6 ): 2.58 (3H,s,- Lit: Dornhagen and Scharf 1985a,b
Me), 3.95 (3H,s,-COOMe), 6.47 (lH,s,H-3),
11.00 (lH,s,-OH)
Lit: Fujikawa et al. 1954 Methyl 3,5-dichloroorsellinate, Methyl 2,4-
dihydroxy-3,5-dichloro-6-methylbenzoate
(3,5-Dichlororsellinsauremethylester,
Methyl 3,5-dichloroeverninate, Methyl 2- 2,4-Dihydroxy-3,5-dichlor-6-
hydroxy-4-methoxy-3,5-dichloro-6- methylbenzoesauremethylester)
methylbenzoate
(3,5-Dichloreverninsauremethylester, 2- C9HsClP4 (251.06)
Hydroxy-4-methoxy-3,5-dichlor-6-
methylbenzoesauremethylester) Me
CIOH IOCl20 4 (265.09) C I * l COOMe
HO 3 OH
Me
CI
C I * l COOMe
5 2
MeO 4 3 OH Needles (n-hexane), mp 117-118C
Cl React: NaOC1 red, FeCl3 purple
Lit: Nolan and Murphy 1940; Fujikawa et al.
1954
Needles (MeOH-H 20), mp 80C
Lit: Nolan and Murphy 1940
Methyl 2,6-dihydroxybenzoate
(2,6-Dihydroxybenzoesauremethylester)
MethyI3,5-dichloro-iso-everninate, Methyl 2-
methoxy-3,5-dichloro-4-hydroxy-6- CSHS04 (168.14)
methylbenzoate
c:t
(3,5-Dichlorisoeverninsauremethylester, 2- OH
Methoxy-3,5-dichlor-4-hydroxy-6-
methylbenzoesauremethylester) COOM
'
CIOH IOCl20 4 (265.09) OH
Yellow crystals, mp 53-55, 54-58C MethyI2,6-dimethoxy-3-chlorobenzoate (2,6-

React: NaOC1 red Dimethoxy-3-chlorbenzoesauremethylester)
IH-NMR (CDCl3 ): 4.08 (3H,s,-COOMe), 6.48
ClOH u CI0 4 (230.64)
(2H,d,J=9Hz,H-3,H-5), 7.27 (lH,t,J=9Hz,H-4),
9.62 (2H,s,2x-OH)
Lit: Portelli 1987; Jiang 1991 a ME?
5~COOMe
Methyl 2,6-dihydroxy-3,5-dichlorobenzoate
(2,6-Dihydroxy-3,5- 4~OME?
dichlorbenzoesauremethylester) Cl
CSH6 Cl2 0 4 (237.03)

Prisms (cyclohexane), mp 84, 89C
IH-NMR (CDC13 ): 3.81, 3.89, 3.92 (3x3H,3xs,3x-
OH
OMe), 6.64 (lH,d,J=8.8Hz,H-5), 7.34 (lH,d,J=
C l * ' COOMe- 8.8Hz,H-4)
5 2 MS, m/z 232 (M+,15%), 230 (45), 20J (32), 199
4 3 OH
(100)
CI Lit: Doyle et al. 1963; Jiang 1991
Crystals (Et2 0), mp 162-165C Methyl 2,6-dimethoxybenzoate

IH-NMR (CDCl3): 4.05 (3H,s,-COOMe), 7.50 (2,6-Dimethoxybenzoesauremethylester)
(lH,s,H-4), 10.01 (2H,s,2x-OH)
ClO H 12 0 4 (196.20)
Lit: Elix and Portelli 1990; Jiang 1991
e:t:
OMe
Methyl 2,4-dihydroxy-3,5,6-trimethylbenzoate
(2,4-Dihydroxy-3,5,6- COOMe
trimethylbenzoesa uremethylester )
OMe-
Cll H 140 4 (210.22)
Prisms (n-hexane), mp 73-78, 88C
Me lH-NMR (CDCIJ: 3.81 (6H,s,2x-OMe), 3.90
(3H,s,-COOMe), 6.55 (2H,d,J=8.8Hz,H-3,H-5),
M e * , COOMe
5 2 7.28 (lH,t,J=8.8Hz,H-4)
H04 3 OH MS, m/z 196 (M+,20%), 165 (100), 150 (20)
ME? Lit: Mauthner 1929; Jiang 1991
Needles (n-hexane), mp 96-97C

IH-NMR (60 MHz, CC14 ): 2.05 (6H,s,2x-Me),
2.33 (3H,s,-Me), 3.87 (3H,s,-COOMe), 5.16,
11.38 (2xIH,2xs,2x-OH)
Lit: Hamilton and Sargent 1976
MethyI2,6-dimethoxy-3,5-dichlorobenzoate Me
(2,6-Dimethoxy-3,5- HO~COOMe
dichlorbenzoesauremethylester)
CIO H IO C1 20 4 (265.09)
MeO~OMe
3
oME? Glistening prisms (CH 2 C12 -n-hexane), mp 112-

113 DC
C l * 1 COOME?
5 2 lH-NMR (lOOMHz,CDC13): 2.13 (3H,s,-Me),
4 3 oME? 3.73 (3H,s,-OMe), 3.96 (6H,s,2x-OMe), 5.32
Cl
(IH,s,-OH), 6.29 (lH,s,H-3)
MS, m/z 226 (M+)
Lit: Sargent et al. 1975
Yellow oil
lH-NMR (CDClJ: 3.88 (6H,s,2x-OMe), 3.95
(3H,s,-COOMe), 7.45 (lH,s,H-4) MethyI3,5-dimethoxy-4-methylbenzoate (3,5-
Lit: Elix and Portelli 1990; Jiang 1991 Dimethoxy-4-methylbenzoesauremethylester)
Cn H l4 0 4 (210.25)
MethyI2,4-dimethoxy-5-formyl-6-
methylbenzoate (2,4-Dimethoxy-5-formyl- 7
6-methylbenzoesauremethylester) Me 0 J . ; f12
6 COO Me
C12HI 40 S (238.23) Me 4 3
8
OMe
Needles (MeOH), mp 103 DC

UV: 212 (4.6),262 (4.2), 298nm (3.6)
IR: 1593, 1714cm-1
lH-NMR (60MHz,CDCiJ: 2.13 (3H,s,-Me), 3.87
(6H,s,2x-OMe), 3.90 (3H,s,-COOMe), 7.20
Plates (CH 2 C1 2 -n-hexane), mp 125-126 DC (2H,s,H-2,H-6)
React: PD yellow 13C-NMR (20.1 MHz,acetone-d6 ): C-1: 129.5, C-
lH-NMR (lOOMHz,CDC13 ): 2.49 (3H,s,-Me), 2: 105.3, C-3: 159.0, C-4: 120.4, C-7: 167.2, C-8:
3.90 (6H,s,2x-OMe), 3.92 (3H,s,-COOMe), 6.38 8.8, -OMe: 56.1, -COOMe: 52.2
(lH,s,H~3), 10.47 (lH,s,-CHO)
MS, mlz 210 (M+, 100%), 179 (66), 151 (32)
MS, m/z 238 (M+) Lit: Achenbach et al. 1985
Methyl 2,4-dimethoxy-5-hydroxy-6-
methylbenzoate (2,4-Dimethoxy-5-hydroxy-6-
Cll H l40 S (226.22)
MethyI2,4-di-O-methyl-3- S-Methyl-di-O-methylorsellinic acid, 2,4-

hydroxyolivetolcarboxylate, Methyl 2,4- Dimethoxy-S,6-dimethylbenzoic acid (5-
dimethoxy-3-hydroxy-6-n -pentylbenzoate Methyl-di-0-methylorsellinsaure,
(2,4-Di-0-methyl-3- 2,4-Dimethoxy-5,6-dimethylbenzoesaure)
hydroxyolivetolcarbonsauremethylester, 2,4-
Cll H l40 4 (210.22)
Dimethoxy-3-hydroxy-6-n-
pentylbenzoesauremethylester)
ME'
C1sH 22 0 S (282.33) ME'~COOH
5'
ME' ME'O ~
4 OME'
Crystals (EtOH-H 20), mp 208-210C

IR (CHCl3): 1595, 1700, 1725, 3140, 3480cm-1
Lit: Canonica et al. 1972
ME'O
Methyl divarate, Methy12,4-dihydroxy-6-n-
propylbenzoate (Divarinsauremethylester, 2,4-
Needles (n-pentane), mp 72-73C Dihydroxy-6-n -propylbenzoesauremethylester)
IR (CCl4 ): 870, 1740, 3600cm-1 Cll H 14 0 4 (210.22)
lH-NMR (60MHz,CDCl3 ): 0.88 (3H,t,Me-5'),
1.37 (6H,m,-CH 2-2'-4'), 2.45 (2H,t,-CH 2-1'), ME'
3.88 (6H,s,-OMe,-COOMe), 5.45 (lH,s,-OH),
6.48 (IH,s,H-5)
1COOMe
Methyl di-O-methylorsellinate, Methyl 2,4- HO" OH
dimethoxy-6-methylbenzoate (Di-O-
methylorsellinsauremeth ylester, Crystals (n-hexane), mp 78C
2,4-Dimethoxy-6- React: NaOCl red
methylbenzoesauremethylester) UV (EtOH): 218,266, 303 nm
Cll H l4 0 4 (210.22) IR (Nujol): 1248, 1265, 1270, 1330, 1550, 1580,
1640, 3300 cm-1
ME' MS, m/z 210 (M+), 178, 150, 122
5~COOME' Lit: Asahina and Akagi 1935
ME'O~OME'
3 Methyl everninate, MethyI2-hydroxy-4-
Prisms (n-pentane), mp 40-43C methoxy-6-methylbenzoate
!3C-NMR (CDCl3 ): C-l: 116.5, C-2: 158.3, C-3: (Everninsa uremethylester, 2-Hydroxy-4-
96.2, C-4: 161.4, C-5: 106.8, C-6: 138.3, C-7: methoxy-6-methylbenzoesauremethylester)
168.7, C-8: 19.9 ClO H 120 4 (196.20)
Lit: Wedekind and Fleischer 1923; Sargent et al.
1975; H6fie et aL 1980
Me 4-0-Methylhaematommic acid, 2-Hydroxy-3-

~COOM. formyl-4-methoxy-6-methylbenzoic acid (4-0-
Methylhaematommsaure,
MeO 4 3 OH 2-Hydroxy-3-formyl-4-methoxy-6-
methylbenzoesaure)
Crystals (MeOH-H 2 0), mp 66-68C CIOH lO 0 5 (210.18)
*
UV (EtOH): 216, 262, 300nm
IH-NMR (200MHz,CDCI3 ): 2.50 (3H,s,-Me), Me
3.83 (3H,s,-OMe), 3.96 (3H,s,-COOMe), 6.32, 6 1 COOH
6.38 (2xlH,2xs,H-3,H-5), 11.78 (lH,s,-OH)
4 2
MS, m/z 196 (M+,42%), 165 (19), 164 (63), 163 MeO 3 OH
(6),137 (9), 136 (100), 135 (12), 121 (5), 108 (23),
CHO
107 (26)
HPLC: Rj 8
Lit: Asahina and Ihara 1929 Crystals (acetone), mp 198-199C (dec.)
React: PD yellow
IH-NMR (200MHz,CDCI3 ): 2.53 (3H,s,-Me),
Methyl haematommate, Methyl 2,4-dihydroxy- 3.96 (3H,s,-OMe), 6.29 (IH,s,H-5), 10.34 (1H,
3-formyl-6-methylbenzoate s,-CHO), 12.41, 12.88 (2xlH,2xs,-OH,-COOH)
(Haematommsauremethylester, 2,4- MS, m/z 210 (M+,66%), 182 (20), 179 (16), 178
Dihydroxy-3-formyl-6- (34), 177 (14), 165 (4), 151 (13), 150 (100), 122
methylbenzoesauremethylester) (31), 121 (9), 108 (4)
CIOH lO 0 5 (210.05) Lit: Asahina and Yanagita 1934
#
Me MethyI2-hydroxy-3-chloro-6-
6 '2 COOME> methoxybenzoate (2-Hydroxy-3-chlor-6-
methoxybenzoesauremethylester)
HO 4 3 OH
C9H 9CI0 4 (216.61)
CHO
OMe
Prisms (EtOAc-n-hexane), mp 144C, needles
(MeOH), mp 146C 5~COOMe
React: KOH yellow, PD yellow
IH-NMR (CDCI3 ): 2.55 (3H,slMe-8), 3.98 (3H,s,- "Y'OH
OMe), 6.32 (1H,s,H-5), 10.37 (lH,s,-CHO), CI
12.45, 12.92 (2xlH,2xs,2x-OH)
MS, m/z 210 (M+,23%), 178 (16), 150 (10), 122 Needles (EtOAc-n-hexane), mp 84-85C
(25), 94 (22), 77 (10), 66 (26) IH-NMR (CDCI3 ): 3.84 (3H,s,-COOMe), 3.96
Deriv: Methyl tetraacetylhaematommate, (3H,s,-9Me), 6.38 (1H,d,J=8.8Hz,H-3), 7.40
prisms, mp 124-125C (CHCI3 -MeOH), from (1H,d,J=8.8Hz,H-4), 12.01 (1H,bs,-OH)
methyl haematommate with Ac20-H 2S04 MS, m/z 218 (M+,4%), 216 (12), 186 (30), 184
Lit: Whalley 1949; Seshadri and Venkata- (100)
subramanian 1959 Lit: Jiang 1991
*
Methyl 3-hydroxydivarate, Methyl 2;3,4- Me
trihydroxy-6-n-propylbenzoate (3- 6 12 COOMe
Hydroxydivarinsauremethylester,
2,3,4-Trihydroxy-6-n- HO 4 3 OH
propylbenzoesauremethylester) OH
CI1 H 140 S (226.22)

Rectangular rods (EtOAc), mp 154-155C
Me React: NaOCI red, Ba(OH)z indigo blue FeCl3
(EtOH) greenish blue
Deriv: Methyl triacetyl-3-hydroxyorsellinate,
COOMe prisms, mp 120-121 C (EtOAc), from methyl 3-
hydroxyorsellinate with AczO-pyridine
HO OH
OH
Methyl 5-hydroxyorsellinate, Methyl 2,4,5-

Crystals (n-hexane), mp 69-70C trihydroxy-6-methylbenzoate (5-
IR (Nujol): 1620, 1660,3450, 3540cm-1 Hydroxyorsellinsauremethylester, 2,4,5-
Trihydroxy-6-methylbenzoesauremethylester)
Methyl 5-hydroxyeverninate, Methyl 2,5- C9HlOOS (198.17)
dihydroxy-4-methoxy-6-methylbenzoate
(5-Hydroxyeverninsauremethyleste~, 2,5-
Me
Dihydroxy-4-methoxy-6-
methylbenzoesauremethylester) HO~1 COOMe
5 2
CIO H 12 0 s (212.20) HO 4 OH
Me Hexagonal plates (EtOAc), mp 205C

HO~COOMe React: Ba(OH)z bright red colour with green
precipitate, FeCl3 (EtOH) transient red
MeO~OH Deriv: Methyl triacetyl-5-hydroxyorsellihate,
mp 146-147, from methyl 5-hydroxyorsel-
linate with AczO-H zS04
Prisms (EtOAc), mp 153-154C
Lit: Asahina and Kusaka 1942; Aghoramurthy
React: FeCl3 (EtOH) bluish green, rapidly fading
and Seshadri 1952
Methyl iso-divaricatinate
Methyl 3-hydroxyorsellinate, Methyl 2,3,4- (Iso-divaricatinsauremethylester)
trihydroxy-6-methylbenzoate (3-Hydroxy-
orsellinsauremethylester, 2,3,4-Trihydroxy- C12 H I6 0 4 (224.25)
6-methylbenzoesauremethylester)
C9H lO OS (198.17)
1
Me Crystals, mp 146C
Lit: Blaser et al. 1992
C:OOMe
2-0-Methyllobaritonic acid, 2,4-Dimethoxy-6-
HO OMe (1' -oxo-n-pentyl)-benzoic acid [2-0-
Methyllobaritonsaure, 2,4-Dimethoxy-6-
Plates (MeOH), mp 121C (1' -oxo-n-pentyl)-benzoesaure]
Lit: Asahina and Hirakata 1932
C14H180S (266.28)
Methyl iso-everninate, MethyI2-methoxy-4-
hydroxy-6-methylbenzoate (Iso-everninsaure-
methylester,2-Methoxy-4-hydroxy-
6-methylbenzoesauremethylester)
CIOH 120 4 (186.20)
8
Me
~~OOMe
4 2 Crystals (benzene), mp 134C
HO OMe Lit: Asahina and Shibata 1954
UV (EtOR): 204 (4.41),250 (3.67),282 nm (3.42) MethyI3-methoxyorsellinate, Methyl 2,4-
lH-NMR (CDC13 ): 2.17 (3H,s,-Me), 3.67 (3H,s,- dihydroxy-3-methoxy-6-methylbenzoate
OMe), 3.90 (3H,s,-COOMe), 6.20 (2H,s,H-3,H- (3-Methoxyorsellinsauremethylester, 2,4-
5),6.91 (lH,s,-OH) Dihydroxy-3-methoxy-6-
J3C-NMR (CDC13 ): C-l: 114.84, C-2,C-4: 158.68, methylbenzoesauremethylester)
158.81, C-3,C-5: 96.95,109.49, C-6: 138.69, C-7: CIO H I2 Os (212.20)
170.22, C-8: 19.81, -OMe, -COOMe: 52.37, 55.67
*
Lit: Koller and Pfeiffer 1933; Howells and Me
Newbold 1965; Djura et al. 1976; Nicollier et al.
6 '2 COO Me
1979a; Dornhagen and Scharf 1985a,b
HO 4 3 OH
Methyl iso-rhizonate, MethyI2-methoxy-3,6- OMe
dimethyl-4-hydroxybenzoate (Iso-rhizon-
sauremethylester, 2-Methoxy-3,6-dimethyl- Needles, mp 90C
4-hydroxybenzoesauremethylester) React: NaOCI red
Cll H l4 0 4 (210.22) lH-NMR (CDCI3 ): 2.47 (3H,s,-Me), 3.94 (6H,s,-
*
OMe,-COOMe), 6.11 (IH,s,HO-4), 6.37 (lH,s,
Me
H-5), 11.94 (IH,s,HO-2)
6 , COOMe MS, m/z 212 (M+,31 %), 180 (84), 165 (25), 152
4 2 (92), 137 (51), 109 (26), 91 (100)
HO 3 OMe Lit: Naidu 1993; Elix et al. 1994b ~
Me
MethyI4-0-methylhaematommate, Methyl Oil

2-hydroxy-3-formyl-4-methoxy-6- IH-NMR (CDC13 ): 0.90 (3H,t,J=6.6Hz,Me-S'),
methylbenzoate 1.32 (4H,m,-CH 2-3',-CH2-4'), 1.53 (2H,m,
(4-0-Methylhaematommsauremethylester, -CH2-2'), 2.84 (2H,t,J=7Hz,-CH 2-1'), 3.80
2-Hydroxy-3-formyl-4-methoxy-6- (3H,s,-OMe), 3.92 (3H,s,-COOMe), 6.92, 6.33
methylbenzoesauremethylester) (2xlH,2xd,J=2.6Hz,H-3,H-S)
Lit: Gonzalez et al. 1991
CllH120s (224.21)
Me
2-0-Methylolivetolcarboxylic acid, 2-Methoxy-
5~COOMe 4-hydroxy-6-n-pentylbenzoic acid (2-0-
Methylolivetolcarbonsaure, 2-Methoxy-
MeOOH
4-hydroxy-6-n-pentylbenzoesaure)
CHO
C13H I8 0 4 (238.27)
IH-NMR (200MHz,CDC13 ): 2.52 (3H,s,-Me),
3.86 (3H,s,-OMe), 3.97 (3H,s,-COOMe), 6.47
(lH,s,H-S), 10.35 (lH,s,-CHO), 12.42 (lH,s,-
OH)
MS, m/z 224 (M+,70/0), 210 (53), 196 (3),182 (17),
179 (B), 178 (31), 163 (2), 151 (12), 150 (lOO), COOH
137 (2), 122 (B), 109 (3)
Lit: Asahina and Simosato 1938 OMe
3
3-0-Methylolivetol, 3-Methoxy-5-n- Needles (benzene), mp 105C

pentylphenol IR (KBr): 722, 830, 844, 945, 1005, 1064, 1116,
see Section 3.7.1, page 162 1158, 1190, 1250, 1310, 1430, 1462, 1500, 1600,
1684, 2900, 2970, 3400 cm- 1
IH-NMR (60MHz,CDC13 -C2DsOD): 0.96 (3H,t,
MethyI4-0-methylolivetolcarboxylate, Methyl Me-S'), 1.10-1.80 (6H,m,-CH 2-2' -4'), 2.70
2-hydroxy-4-methoxy-6-n-pentylbenzoate (4- (3H,t,J=7Hz,-CH 2-1'), 3.88 (3H,s,-OMe), ,6.35
0-Methylolivetolcarbonsauremethylester, 2- (2H,s,H-3,H-S)
Hydroxy-4-methoxy-6-n- Lit: Asahina and Nogami 1942
pen tylbenzoesa uremethylester)
Cl4B2004 (252.30) 4-0-Methylolivetolcarboxylic acid, 2-Hydroxy-
4-methoxy-6-n-pentylbenzoic acid (4-0-
Methylolivetolcarbonsaure, 2-H ydroxy-
4-methoxy-6-n-pentylbenzoesaure)
see 'Section 3.7.1, page 159
1 COOMe
OH
3
2-0-Methylolivetonic acid, 2-Methoxy-4-

0
2-0-Methylolivetonide, Lactone of 2-methoxy-
hydroxy-6-(2'-oxo-n-heptyl)-benzoic acid 4-hydroxy-6-(2' -hydroxy-n-hept-l' -enyl)-
[2-0-Methylolivetonsaure, 2-Methoxy-4- benzoic acid [2-0-Methylolivetonid, Lacton
hydroxy-6-(2'-oxo-n-heptyl)-benzoesaure] der 2-Methoxy-4-hydroxy-6-(2'-hydroxy-n-
hept-l'-enyl)-benzoesaure]
ClsHzoOs (280.31)
ClsHlS04 (262.29)
Me
Me
1 COOH
OMe
Prisms (H 20), mp 119-120C

Lit: Asahina and Fuzikawa 1935b Needles (benzene), mp 146-147C
4-0-Methylolivetonic acid, 2-Hydroxy-4- 4-0-Methylolivetonide, Lactone of 2-hydroxy-

methoxy-6-(2'-oxo-n-heptyl)-benzoic acid 4-methoxy-6-(2'-hydroxy-n-hept-l' -enyl)-
[4-0-Methylolivetonsaure, 2-Hydroxy-4- benzoic acid [4-0-Methylolivetonid, Lacton
methoxy-6-(2'-oxo-n-heptyl)-benzoesaure] der 2-Hydroxy-4-methoxy-6-(2'-hydroxy-n-
hept-l' -enyl)-benzoesaure]
ClsH200S (280.31)
C1sHlS04 (262.29)
Me
Me
Prisms (benzene), mp 94-95C

Deriv: Methyl 4-0-methylolivetonate, needles, Needles (MeOH), mp 57C
mp 80C (n-hexane), from 4-0-methylolive- React: FeCl3 (EtOH) violet
tonic acid with CH2 N2 IR (KBr): 700, 738, 766, 810, 835, 862, 890, 960,
Lit: Asahina and Fuzikawa 1935b 984, 1048, 1078, 1160, 1206, 1246, 1294, l312,
l346, l392, 1434, 1468, 1518, 1572, 1640, 1670,
2980, 3100 cm-1
MS, m/z 262 (M+,1000/0), 248 (9), 233 (17), 191 2-0-Methylrhizonic acid, Di-O-methyl-~
(37),177 (25), 164 (98), 150 (10), 135 (29) orcinolcarboxylic acid, 2,4-Dimethoxy-3,6-
Lit: Asahina and Nogami 1942 dimethylbenzoic acid (2-0-Methylrhizonsaure,
Di -0-methyl- ~-orcinolcarbonsaure, 2,4-
Dimethoxy-3,6-dimethylbenzoesaure)
Methyl ~-orcinolcarboxylate, Methyl 2,4-
dihydroxy-3,6-dimethylbenzoate Cl1 H l4 0 4 (210.22)
(~-Orcinolcarbonsauremethylester,
Me
2,4-Dihydroxy-3,6-
dimethylbenzoesauremethylester) 5h eoOH
see Section 3.7.1, page 160 MeO~OMe

Me
5-Methyl-~-orcinolcarboxylic acid, 2,4-
Crystals (benzene), mp 106 D C
Dihydroxy-3,5,6-trimethylbenzoic acid IR (KBr): 1690, 3050 cm- 1
(5- Methyl-~-orcinolcarbonsaure, 2,4- IH-NMR (270MHz,CDCIJ: 2.14 (3H,s,Me-2),
Dihydroxy-3,5,6-trimethylbenzoesaure) 2.59 (6H,s,Me-3,Me-6), 3.84 (2H,s,MeO-4),
CIOH12 0 4 (196.20) 3.87 (3H,s,MeO-2), 6.58 (1H,s,H-5)
MS, m/z 210 (M+,710/0), 193 (49), 177 (30), 163
(29), 150 (11), 149 (42)
Me
Deriv: Methyl 2-0-methylrhizonate, mp 145 DC,
M e # ,COOH from 2-0-methylrhizonic acid with CH2N2
5 2
Lit: Nishitoba et al. 1987
HO 4 3 OH
Me
Methyl 2,4,5-trimethoxy-6-methylbenzoate
(2,4,5-Trimethoxy-6-
Crystals (EtOAc-n-hexane), mp 192-193 DC
React: NaOCI red
UV (MeOH): 264 (3.07), 310nm (3.64); MeOH + C12HI 6 0 S (240.25)
NaOH: 256 (3.84), 302nm (3.69) Me
IR (KBr): 1620,2860, 3500cm-1
IH-NMR (DMSO-d6 ): 2.08 (6H,s,2x-Me), 2.40 Meo~, eOOMe
5 2
(3H,s,-Me), 9.17 (3H,bs,3x-OH)
MeO 4 OMe
Deriv: 5-Methyl-diacetyl-~-orcinolcarboxylic
acid, from 5-methyl-~~orcinolcarboxylic acid Crystals, mp 69-71 DC
with Ac 2 0-Py
Lit: Andres et al. 1967
(+)-Montagnetol
Methyl orsellinate, Methyl 2,4-dihydroxy-6-
methylbenzoate (Orsellinsauremethylester,
2,4-Dihydroxy-6- Olivetol, 2,4-Dihydroxy-6-n-pentylbenzene
methylbenzoesauremethylester) (2,4-Dihydroxy-6-n-pentylbenzen)
see Section 3.7.1, page 160 see Section 3.7.1, page 161
Olivetolcarboxylic acid, 2,4-Dihydroxy-6-n- Needles (benzene), mp 110C

pentylbenzoic acid (Olivetolcarbonsaure, 2,4- React: NaOCI deep red, FeCl3 (EtOH) purple
Dihydroxy-6-n-pentylbenzoesaure) IR (KBr): 702, 804, 858, 972, 1070, 1112, 1146,
1170, 1190, 1240, 1260, 1380, 1482, 1620, 1660,
2850, 2950, 3220 cm-1
IH-NMR (200MHz,CDCI3 ): 0.90 (3H,t,Me-7'),
Olivetonic acid, 2,4-Dihydroxy-6-(2'-oxo-n- 1.33 (4H,m,-CH 2-4',-CH 2-5'), 1.67 (2H,m,
heptyl)-benzoic acid [Olivetonsaure, 2,4- -CH2-6'), 2.48 (2H,t,-CH 2-3'), 6.18 (lH,s,H-1'),
Dihydroxy-6- (2'-oxo-n-heptyl)-benzoesaure 1 6.30,6.44 (2x1H,2xd,H-3,H-5)
MS, mlz 248 (M+,100%), 230 (9),215 (9), 193 (8),
C14H1SOS (266.28) 192 (68), 191 (4), 177 (20), 164 (6),163 (24), 151
(12),150 (98),122 (4), 121 (34),81 (12),69 (14),
Me 65 (8),43 (1)
Lit: Asahina and Asano 1932
Orcinol, 3,5-Dihydroxytoluene
(3,5-Dihydroxytoluen)
J3-0rcinol, 2,4-Dihydroxy-3,6-dimethylbenzene
Crystals (H 2 0), mp 159-160C
(2,4-Dihydroxy-3,6-dimethylbenzen)
Deriv: Methyl olivetonate, mp 85-86C (ben- see Section 3.7.1, page 162
zene-n-hexane), from olivetonic acid with the
calculated amount of CH 2N2 in Et20 at OC
Orcinolaldehyde, 2,4-Dihydroxy-6-
Lit: Asahina and Asano 1932
methylbenzaldehyde (Orcinolaldehyd, 2,4-
Dihydroxy-6-methylbenzaldehyd)
Olivetonide, Lactone of 2,4-dihydroxy-6-(2'-
CSH S03 (152.14)
hydroxy-n-hept-l'-enyl)-benzoic acid
11'
[Olivetonid, Lacton der 2,4-Dihydroxy-6-(2'-
hydroxy-hept -1' -enyl)-benzoesaure1 Me
C14H1604 (248.27) CHO

4 2
HO OH
7'
Me
Crystals (H 2 0), mp 179-180 C, pale brown crys-
tals (cyclohexane), mp 180-183C
IH-NMR (CDCI3): 2.52 (3H,s-Me), 6.21 (2H,s,H-
3,H-5), 10.09 (lH,s,-CHO), 12.35, 13.04 (2x1H,
2xs,2x-OH)
Lit: pfau 1933; Jiang 1991
~-Orcinolaldehyde,2,4-Dihydroxy-3,6- Crystals, mp 48-49, 54-55C

dimethylbenzaldehyde (~-Orcinolaldehyd, 2,4- lH-NMR (CDCI3): 3.76 (9H,s,3x-OMe), 6.08
Dihydroxy-3,6-dimethylbenzaldehyd) (3H,s,3xarom.-H)
MS, m/z 168 (M+,100%), 139 (84), 125 (20)
C9H lO 0 3 (166.17)
4
Lit: Buckingham 1994b
Me
1 CHO Rhizonic acid, 4-0-Methyl-~-orcinolcarboxylic
4 2 acid, 2-Hydroxy,3,6-dimethyl-4-methoxy-
HO OH
benzoic acid (Rhizoninsaure, 4-0-Methyl-~
Me orcinolcarbonsaure,2-Hydroxy-3,6-
dimethyl-4-methoxybenzoesaure)
Glistening needles (EtOH-H 2 0), mp 166C
React: NaOC1 red, PD yellow ClO H I2 0 4 (196.20)
5h
Lit: Sonn 1931a 9
~-Orcinolcarboxylic acid, 2,4-Dihydroxy-3,6- toOH

dimethylbenzoic acid (~-Orcinolcarbonsaure, MeOOH
2,4-Dihydroxy-3,6-dimethylbenzoesaure) Me
see Section 3.7.1, page 162 a
Crystals (EtOH-H 20), mp 196C (heated
slowly), 235C
Orcinolmonomethylether UV (MeOH): 220, 264, 304nm
see Section 3.7.1, page 163 IR (KBr): 880,1224,1264,1380, 1420, 1500, 1570,
1605, 1620-1650,2400,2860, 2970cm-1
lH-NMR (270MHz,CDCI3 ): 2.00 (3H,s,Me-8),
~-Orcinolmonomethylether, 2,5-Dimethyl-3- 2.59 (3H,s,Me-9), 3.89 (3H,s,-OMe), 6.48 (1H,
methoxyphenol s,H-5)
see Section 3.7.1, page 163 13C-NMR (pyridine-ds): C-1: 107.2, C-2: 163.3,
C-3: 11004, C-4: 161.3, C-5: 105.8, C-6: 141.1,
C-7: 175.9, C-8: 804, C-9: 24.6, C-4-0Me: 5~A
Orsellinic acid, 2,4-Dihydroxy-6- MS, m/z 196 (M+,98%), 165 (67), 164 (100), 163
methylbenzoic acid (Orsellinsaure, 2,4- (22), 137 (6),136 (45),122 (3), 121 (14),108 (7),
Dihydroxy-6-methylbenzoesaure) 93 (14),77 (9), 65 (9),51 (6),39 (8)
see Section 3.7.1, page 163 Deriv: Methyl rhizonate, mp 104-105 C (EtOH),
from rhizonic acid with the calculated amount
of CH2N 2 in Et2 0
Phloroglucinoltrimethylether Lit: Tsuda et al. 1980; Nishitoba et al. 1987
C9H I2 0 3 (168.19)
OMe
Sphaerophorol,2,4-Dihydroxy-6-n-
heptylbenzene (2,4- Dihydroxy-6-n-
M.O~OM. heptylbenzen)
C13H2002 (208.29)
7' Succinic acid (Bernsteinsaure)

Me
C4H 6 0 4 (l18.08)
6'
Prisms (H 2 0), mp 185C

Deriv: Dimethyl succinate, mp 19C, from suc-
OH cinic acid with CH2 N2
Lit: Buckingham 1994c
Needles or leaflets (H 2 0), mp 57-58C
React: NaOCI red
IR (KBr): 1150, 1610,2870,2940, 3350cm-1 Tert-butyI5-chlorohaematommate, Tert-butyl
IH-NMR (200MHz,CDCI 3): 0.88 (3H,t,Me-7'), 2,4-dihydroxy-3-formyl-5-chloro-6-methyl-
1.30 (8H,m,-CH 2-3' -6'), 1.67 (2H,m,-CH z-2'), benzoate (5-Chlorhaematommsaure-tert-
2.50 (2H,t,-CH z-l'), 6.10-6.50 (3H,m,H-l,H- butyl ester , 2,4-Dihydroxy-3-formyl- 5-chlor-
3,H-5) 6-methylbenzoesaure-tert -butyl ester )
MS, mlz 208 (M+,41 0/0), 166 (11), 152 (3), 137 C13HI 5 ClO s (286.70)
(25),124 (100), 123 (40), 111 (6)
Lit: Asahina and Hashimoto 1934; Asahina and
9
Shibata 1954 Me 7
CI # 1 COOC(Me)3
Sphaerophorolcarboxylic acid, 2,4-Dihydroxy- 5 2
6-n-heptylbenzoic acid (Sphaerophorol- HO 4 3 OH
carbonsaure, 2,4-Dihydroxy- CHO
6-n-heptylbenzoesa ure) 8
C14Hzo04 (252.30)
Needles (n-hexane), mp 108-109C
Me React: PD yellow
IR (KBr): 716, 850, 1048, 1164, 1208, 1262, 1340,
1390, 1410, 1440, 1590, 1648, 2800, 3030,'
3500cm-1
IH-NMR (l00MHz,CDC13 ): 1.60 [9H,s,-C(Me)3]'
2.63 (3H,s,-Me), 10.25 (lH,s,-CHO), 12.5-13.1
(2H,bs,2x-OH)
Lit: H uneck 1984b
. Crystals (benzene), mp 130-135, 142-144C

Tert-butyl everninate, Tert-butyI2-hydroxy-4-
React: NaOCI red, FeCl3 red-violet
methoXy-6-methylbenzoate (Everninsaure-
IR (KBr): 1260, 1450-1480, 1630, 2870, 2940,
tert-butylester,2-Hydroxy-4-methoxy-
3350cm-1
6-methylbenzoesaure-tert -butylester)
Lit: Harris and Carney 1967; Durrani and
Tyman 1980; Dyke et al. 1987 C13H I8 0 4 (238.27)
A'
Me 5'
Me
COOC(Me)3
ME'O " 2 OH
, COOC(Me)3
Crystals (n-pentane), mp 28 DC 2
IR (KBr): 70,0,,758,818,850,,952,992,10,40,,10,62, 3
OH
1118, 1160" 120,0" 1262, 130,0" 1330" 1370" 1420"
1450,,1576, 1610, 1640"30,0,0,, 345o'cm-1 Oil
IR (film): 710" 754, 780" 820" 832, 850"960,, 10,42,
IH-NMR (2o'o'MHz,CDCI3): 2.80, (9H,s,-C(Me)3)'
3.45 (3H,s,-Me), 4.45 (3H,s,-OMe), 6.39, 6.45 1110" 1154, 1194, 1260" 130,0" 1330" 1370" 1422,
(2XIH,2xd,H-3,H-5) 1462,1570" 160,6, 1636,2970" 34o'o'cm- I
IH-NMR (lOo'MHz,CDCI 3): 0,.83 (3H,t,Me-5'),
Lit: Huneck 1984b
1.28 (6H,m,-CH z-2' -5'), 1.56 [9H,s,-C(Me)3]'
2.80, (2H,t,-CH z-l'), 6.17, 6.23 (2XIH,2xd,H-3,
Tert-butyl haematommate H-5), 11.84 (lH,s,-OH)
(Haematommsaure-tert -butylester) Lit: Huneck 1984b
C13 H 1Ps (252.26)
Tert-buty14-0-methylolivetonate, Tert-butyl
9 2-hydroxy-4-methoxy-6-(2'-oxo-n-heptyl)-
ME' benzoate [4-0-Methylolivetonsaure-
NCOOCCMe)3 tert-butylester, 2-Hydroxy-4-methoxy-6-(2'-
oxo-n -heptyl)-benzoesaure-tert-butylester]
HO~OH C l9 HzsOs (336.41)
CHO
7'
Me
Crystals, mp 119-12O, D C
React: N aOCI red, PD yellow
IR (KBr): 810" 1180" 1660,,2870,,2980,,3450, cm- I
IH-NMR (CCI 4 ): 1.63 [9H,s,-C(Me)3]' 2.52 (3H,
s,Me-9), 6.27 (lH,s,H-5), 10,.38 (lH,s,-CHO), , COOC(Me)3
12.40" 13.28 (2xlH,2xs,2x-OH)
TLC: Rp 0,.75 (SiO z, CHCl3 with 10,% MeOH) OH
Lit: Bachelor et al. 1979 Oil
IR (film): 754, 820" 850" 960" 10,46, 1114, 1154,
1198, 1266, 130,4, 1334, 1374, 1428, 1464, 1572,
Tert-butyI4-0-methylolivetolcarboxylic acid,
1610" 1640" 170,8,2990" 340,0, cm- I
Tert-butyI2-hydroxy-4-methoxy-6-n-
IH-NMR (lo'o'MHz,CDCI3): 0,.80, (3H,t,Me-7'),
pentylbenzoate (4-0-
1.20, (6H,m,-CH z-4' -6'), 1.50, (9H,s,-C(Me)3)'
Methylolivetolcarbonsaure-tert -butylester,
2.34 (2H,t,-CH z-3'), 3.72 (3H,s,-OMe), 3.93
2-Hydroxy-4-methoxy-6-n -pentylbenzoesaure-
(2H,s,-CH z-l'), 6.13, 6.32 (2XIH,2xd,H-3,H-5),
tert -butylester)
11.64 (lH,s,-OH)
C17 HZ6 0 4 (294.38) Lit: Huneck 1984b
Tert-butyl ~-orcinolcarboxylate, Tert-butyl Tert-butyl rhizonate, Tert-butyI2-hydroxy-

2,4-dihydroxy-3,6-dimethylbenzoate 3,6-dimethyl-4-methoxybenzoate
(~-Orcinolcarbonsaure- tert -butylester, 2,4- (Rhizonsaure-tert-butylester, 2-Hydroxy-3,6-
Dihydroxy-3,6-dimethylbenzoesaure-tert - dimethyl-4-methoxybenzoesaure-tert-
butylester) butylester)
Cl4HlS04 (250.28) Cl4Hzo04 (252.30)
*
9
Me 9
6 1 ~OOC(Me)3 Me
4 2 h,~OOC(Me)3
HO 3 OH
Me MeO~OH
8 Me
Prisms (EtzO-n-hexane), mp 128-130C 8
IR (KBr): 730, 842, 966, 1024, 1058, 1100, 1140,
1158, 1248, 1300, 1368, 1394, 1430, 1450, 1590, Prismatic plates (n-hexane), mp 68-70C
1620, 1640,3000, 3480cm- 1 IR (KBr): 830, 854, 968, 1000, 1030, 1060, 1130,
IH-NMR (IOO MHz,CDCI3): 1.55 [9H,s,-C(Me)3], 1156, 1180, 1228, 1248, 1300, 1370, 1402, 1446,
2.04 (3H,s,Me-8), 2.36 (3H,s,Me-9), 5.50 (IH, 1460, 1498, 1572, 1616, 1638,2950, 3300cm-1
bs,HO-4), 12.18 (IH,s,HO-2) IH-NMR (100 MHz,CDCIJ: 1.59 [9H,s,-C(MeU,
Lit: Huneck 1984b 2.04,2.48 (2x3H,2xs,2x-Me), 3.80 (3H,s,-OMe),
6.19 (lH,s,H-5), 11.90 (lH,s,-OH)
MS, mlz 252 (M+,34%), 197 (83), 178 (100), 150
Tert-butyl orsellinate, Tert-butyI2,4- (91), 135 (I8), 122 (21), 107 (27)
dihydroxy-6-methylbenzoate Lit: Bachelor et al. 1979; Huneck 1984b
(Orsellinsaure-tert -butylester, 2,4-Dihydroxy-
6-methylbenzoesaure-tert -butylester)
Thamnol, 2,3,6-Trihydroxy-4-
C12 H I60 4 (224.25) methylbenzaldehyde
Me (2,3,6-Trihydroxy-4-methylbenzaldehyd)
'
hCOOC(Me)3
CSH S04 (168.14)
HO ~ OH
Crystals (EtOH), mp 155-156C
UV (EtOH): 218, 266, 305 nm
IR (Nujol): 750, 830,990, 1210, 1280, 1380, 1440,
1518, 1570, 1610, 1640,2840, 3300cm-1
Me
4
4
OH
3
OH
2
CHO
OH
IH-NMR (90MHz,DMSO-d6): 1.65 [9H,s,-C

(Me)3], 2.50 (3H,s,Me-8), 6.25 (2H,s,H-3,H-5), Deep yellow needles (benzene), mp 185C
9.50, 11.90 (2x1H, 2xs, 2x-OH) React: NaOCl red, PD yellow, FeCl3 (EtOH)
Deriv: Tert-butyl-diacetylorsellinate, mp 92- green
93C, from tert-butyl orsellinate with AczO-Py IR (KBr): 1630, 1663, 3220, 3420 cm- l
Lit: Meyappan et al. 1981 Lit: Asahina and Fuzikawa 1932a
3,4,5-Trihydroxytoluene Crystals (n-hexane), mp 71-72 C

(3,4,5-Trihydroxytoluen) UV (EtOH): 273 (3.02),278 (3.04), 291 nm (3.03)
lH-NMR (60MHz,CDCI3 ): 2.08 (6H,s,2x-Me),
C7Hs 03 (140.13)
2.23 (3H,s,-Me), 3.76 (3H,s,-OMe), 4.60 (1H,s,-
OH), 6.29 (lH,s,H-4)
2,4,6-Trimethylorcinol
C9H 12 0 2 (152.19)
Me
Needles (benzene), mp 124C ME'3:s Me
Lit: Koller and Hamburg 1935 4 1
HO 3 2 OH
Me
2,5,6-Trimethyl-3-methoxyphenol
C lO H 1P2 (166.21)
Prisms (benzene), mp 148C
Lit: Whalley 1949
Me
Me~l
5 2
OH
3 Me
OMe
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Addenda
Naphtaquinones Anthraquinones
Squamarone (Squamaron) Erythroglaucinic acid (Erythroglaucinsaure)
C13H120s (248.23) CI 7H120S (344.27)
OH 0 OH
M'O~COOH
13
Me
o OH
Orange-red needles (acetone), mp 275-277C

React: KOH blue-violet Orange crystals (acetone), mp 244-246C
UV (MeOH): 266 (3.85), 321 nm (3.55), MeOH + React: Mg(OAc)2 in EtOH purple
NaOH: 291 (4.05),371 nm (3.49) StL: Xanthoria mandschurica (Zahlbr.) Asah.
MS, m/z 248 (M+), 233, 220, 205, 177 Lit: Nakano et al. 1972
Deriv: Triacetylsquamarone, yellow needles,
mp 145-147C (CHCI3 -MeOH), by acetylation
of squamarone with ACzO-H zS04 lH-NMR 1,6,8-Trihydroxy-3-methyl-5, 7-dichloro-9-
(500MHz, CDCI3 ): 1.11 (3H,t,J=7.5Hz,Me-13), anthrone (1,6,8-Trihydroxy-3-methyl-5,7-
2.04 (3H,s,Me-11), 2.37, 2.38, 2.49 (3x3H,3xs, dichlor-9 -anthron)
3x-OAc), 2.58 (2H,q,J=7.5Hz,-CH 2-12), 7.76 CisHlOCl204 (325.14)
(lH,s,H-9). 13C-NMR (125.7MHz, CDCI3 ): C-1:
176.5, C-2:150.0, C-3: 137.1, C-4: 182.7, C-5:
120.9, C-6: 149.3, C-7: 137.:J, C-8: 153.3, C-9: OH 0 OH
119.1, C-I0: 130.8, C-11: 10.1, C-12: 18.6, C-13:
Cl@
9 18
13.2, -O-{;.O-Me: 167.4, 168.1, 168.9, -O-CO- 6 3
Me: 20.3, 20.8, 21.0 HO 5 Me
StL: parasitic fungus on Squamarina Cl H H
cartilaginea (With.) P. James from the Canary
Islands
TLC: RF 0.45 (n-hexane: EtzO: HCOOH = Physical data unknown
30: 20: 6) StL: Heterodermia obscurata (Nyl.) Trev.
Lit: Himmelreich et al. 1994 Lit: Yosioka et al. 1968b
476 Addenda
Sesquiterpenoids Oil, bplS 117-124C, [am - 11.1 (CHCI 3)

~-Caryophyllene, ~-humulene StL: Evernia prunastri (1.) Ach.
(~-Caryophyllen, ~- Humulen) Lit: Gavin et al. 1978
C1s H 24 (204.34)
Farnesane(Farnesan)
C1sH 32 (212.41)
Me Me Me
Me
~Me
(- )-(E)-~-caryophyllene
Oil, bplS 126.5C
Oil, bP9 118-119C, [am - 15.0 (CHCIJ StL: Evernia prunastri (1.) Ach.
StL: Evernia prunastri (1.) Ach. Lit: Gavin et al. 1978
~-Gurjunene (~-Gurjunen)
a-Copaene (a-Copaen)
C1s H 24 (204.34)
C1s H 24 (204.34)
CJ.:LM'
Me Me
(+ )-gurjunene
Oil, bP13 120-123 DC, [am + 81.8
(-)-a-copaene
Oil, bp 246-251C, [a]D - 13.3 (CHCI3), nbo Lit: Gavin et al. 1978
1.4722
Longifolene (Longifolen)
C1s H 24 (204.34)
~-Elemene (~-Elemen)
Me
C1s H 24 (204.34)
H2C~
H2C~Me
Me CH2 Me
(- )-~-elemene (+ )-longifolene
Addenda 477
Oil, bp36 ISO-151C, [a]D + 41.05 Oil, bpl2 121-122C, [a]D - 79.7
StL: Evernia prunastri (1.) Ach. StL: Evernia prunastri (1.) Ach.
Lit: Gavin et al. 1978 Lit: Gavin et al. 1978
a-Muurolene (a-Muurolen) Triterpenoids

Cerin
C1s H 24 (204.34)
HO
(-)-a-muurolene o
Oil, bp13 1l8C, [ali? - 52.5, nil 1.5051
Lit: Gavin et al. 1978 Plates (CHCI3 or benzene), mp 247-251 C, [a]D
- 46 (CHCI3)
StL: Flavocetraria nivalis (L.) Kamef. et Then
~-Selinene (~-Selinen) Lit: Bruun 1969
C1sH 24 (204.34)
Hopan-II ~,22-diol
~M'
CH 2 CH 2
C30HS002 (444.72)
(+ )-~-selinene
Oil, hP6 121-122 C, [a]D + 61
Needles (EtOH-H 20), mp 216-217C (dec.),
[am + 27.1 (CHCIJ
Thujopsene (Thujopsen) IR: 3300 em-I
C1s H 24 (204.34) IH-NMR (CDCI 3 ): 0.78, 0.80, 0.86, 0.99, 1.05,
1.17, 1.18, 1.21 (8xs,8x3H,8x-Me), 3.87 (lH)
(-)-thujopsene
Subject Index
Abbreviations 125 Acids 141-154

Acaranoic acid 141 Acroscyphan 131
Acarenoic acid 141 Activity against human immunodeficiency virus 4
25a-Acetoxy-20(S),24(R)-epoxydammaran-3fJ-ol 362 Aipolic acid 370
3fJ-Acetoxyfern-9(11)-en-12fJ-ol 362 Alectorialic acid 311
3fJ-Acetoxyfern-9(11)-en-19fJ-ol 363 Alectorialin 312
12a-Acetoxyfern-9(11)-en-3fJ-ol 363 a-Alectoronic acid 314
3fJ-Acetoxyfern-9(11)-en-12-one 364 fJ-Alectoronic acid 229
3fJ-Acetoxyhopan-lfJ,22-diol 364 Alectosarmentin 218
6a-Acetoxyhopan-7fJ,22a-diol 365 Alkanes 137
6a-Acetoxyhopan-16fJ,22-diol 365 Allantoin 126
7fJ-Acetoxyhopan-6a,22-diol 365 Allergenic activity 4
16fJ-Acetoxyhopan-6a,22-diol 366 allo-Protolichesterinic acid 142
20a-Acetoxyhopan-6a,22-diol 366 Allorhizin 314
6a-Acetoxyhopan-22-o1 366 Amphistictinic acid 368
7fJ-Acetoxyhopan-22-ol 367 a-Amyrenone 372
15a-Acetoxyhopan-22-o1 367 fJ-Amyrenone 372
16fJ-Acetoxyhopan-22-ol 367 a-Amyrin 371
15a-Acetoxy-22-hydroxyhopan-24-oic acid 368 fJ-Amyrin 371
19-Acetoxylichesterinic acid 141 a-Amyrone 372
19-Acetoxyprotolichesterinic acid 142 fJ-Amyrone 372
3-Acetoxy -3,4-secostict-4( 23) -en-22a-ol 368 Anagardianic acid 142
3a-Acetoxystictan-2a,22a-diol 369 Antheraxanthin 396
2a-Acetoxystictan-3fJ,22a-diol 368 Anthraquinones 168-183
3fJ-Acetoxystictan-22a-ol 369 Anthrones 168-183
Acetylation 109 Antibiotic activity 3
4-Acetyl-4' -butyrylscabrosin 126 Antitumor and antimutagenic activity 3
a- Acetylconstictic acid 313 Anziaic acid 237
4-Acetyr4' -hexanoylscabrosin ,126 Aphthosin 302
a-Acetylhypoconstictic acid 313 Arabinose 131
Acetyl-iso-arborinol 369 D-Arabitol 131
16-0-Acetylleucotylic acid 369 Argopsin 314
5-0-Acetyl-4-0-methylthiasic acid 302 Arthogalin 126
Acetylportenol 136 Arthoniaic acid 238
3-0-Acetylpyxinol 370 Arthonin 127
a- Acetylsalazinic acid 313 Arthothelin 190
2-0-Acetyltenuiorin 302 Asahinin 168
Acetyl-a-tocopherol 185 Ascomatic acid 218
Acetyltylolupenol B 370 Asemone 190
Acetylzeorin 366 Aspicilin 13 7
480 Subject Index
Astaxanthin 396 Canarione 165

Atranol 155 Canesolide 230
Atranolmonomethylether 403 Canthaxanthine 396
Atranorin 238 Caperatic acid 143
Averantin 169 Caproic acid 143
Averythrin 169 Caprylic acid 143
Carbohydrates 131-136
Bakkenolide A 359 a-Carotene 396
Baeomycesic acid 239 p-Carotene 397
Barbatic acid 239 y-Carotene 397
Barbatol 403 Carotenoids 396-399
Barbatolic acid 312 (-)-Carvone 357
Barbatolin 312 p-Caryophyllene Addenda
Bellidiflorin 169 Cerevisterol 388
Benzene 164 Cerin Addenda
Benzoic acid 155 Cetrariastrumin 324
Benzoquinones 164 Cetraric acid 315
Benzyldepsides 311-312 Chemotaxonomy of lichens 6-9
Benzyl 2,4-dihydroxy-6-methylbenzoate 404 Chiodectonic acid 165
Benzyl esters 111 Chloroatranol 155
Benzyl ethers 112 Chloroatranorin 241
Benzylorsellinate 404 5-Chloro-4-0-demethylbarbatic acid 241
Biodeterioration 6 3-Chloro-2,6-dihydroxybenzoic acid 404
Biological activities of lichen substances 3-4 1-Chloro-2,4-dimethoxy-6-methylbenzene 164
Biological meaning of lichen substances 5 3-Chloro-2,6-dimethoxybenzoic acid 404
Biphenylquinones 183 2-Chloro-3,5-dimethoxyphenol 404
Biphenyls 236 4-Chloro-3,5-dimethoxyphenol 405
Biruloquinone 184 3-Chlorodivaricatic acid 242
Bis-anthraquinones 168-183 5-Chlorodivaricatic acid 242
Bis-anthrones 168-183 5-Chlorodivaricatinic acid 405
Bis-(2,4-dihydroxy-6-n-propylphenyl)-methane 236 7-Chloroemodin 169
Bis-naphthaquinones 164-168 3-Chloroeverninic acid 405
7,7' -Bis-(2,5,6,8-tetrahydroxy-3-ethylnaphtha-1 ,4- Chlorogranulatin 315
quinone) 164 5-Chlorohaematommic acid 405
7,7' -Bis-( 1,4,5,8-tetrahydroxy-3-ethylnaphtha-2,6- 3-Chloroimbricaric acid 243
quinone) 164 Chlorolecideoidin 316
Bis-(p-tolyl)-1,2-ethane 164 2-Chlorolichexanthone 191
Bis-xanthones 190-218 4-Chlorolichexanthone 191
Binonic acid 240 5-Chlorolichexanthone 191
Borneol 356 7-Chlorolichexanthone 192
Bourgeanic acid 143 2-Chloro-3-methoxy-5-methylphenol 164
Brassicasterol 388 2-Chloro-3-0-methylnorlichexanthone 192
Brialmontin 1 240 2-Chloro-6-0-methylnorlichexanthone 192
Brialmontin 2 240 4-Chloro-3-0-methylnorlichexanthone 193
Bromobenzene 164 4-Chloro-6-0-methylnorlichexanthone 193
Buellolide 230 5-Chloro-3-0-methylnorlichexanthone 217
5-Chloro-6-0-methylnorlichexanthone 193
Caloploicin 315 7-Chloro-3-0-methylnorlichexanthone 194
Calycin 399 7-Chioro-6-0-methylnorlichexanthone 194
Campesterol 388 3-Chloro-4-0-methylolivetolcarboxylic acid 405
Camphene 357 2-Chloro-5-0-methylorcinol 164
Camphor 357 l' -Chloronephroarctin 243
Subject Index 481
2cChioronorlichexanthone 194 Cryptostictic acid 321

4-Chloronorlichexanthone 195 j3-Cryptoxanthin 397
5-Chloronorlichexanthone 195 Culture of lichens and their symbionts 9
7-Chloronorlichexanthone 195 Cyclographin 321
5-Chloro-fJ-orcinolcarboxylic acid 406 Cyclohexanol 141
2-Chloroorcinoldimethylether 164 Cyclopaldic acid 406
5-Chloroorsellinic acid 406 p-Cymene 357
l' -Chloropannarin 314 Cynodontin 170
3-Chloroperlatolic acid 244
Chlorophyllopsorin 316 Decane 140
5-Chlororhizonic acid 406 Decarboxythamnolic acid 245
3-Chlorostenosporic acid 243 3-Dechlorodiploicin 321
Chlorovinetorin 196 3-Dechlorogangaleoidin
Cholesta-3,5-dien-7-one 389 3' -Dechlorolecideoidin 322
Cholestan-3fJ-ol 389 3-Dechloro-4-0-methyldiploicin 322
Cholesterol 389 2-Dechloro-8-0-methylthiomelin 196
Choline sulphate 127 4-Dechloro-8-0-methylthiomelin 196
Chromanes 185-190 Dechloropannarin 32
Chromones 185-190 2-Dechlorothiomelin 197
Chrysophanol 170 4-Dechlorothiomelin 197
1,8-Cineol 357 5-Dechlorovicanicin 323
Citreorosein 170 Dec-1-yne 140
Cleavage of depsides 112, 123 4-0-Demethylbaeomycesic acid 245
Cleavage products of depsides and depsidones 4-0-Demethylbarbatic acid 246
403-404 Demethylchodatin 197
Clionasterol 389 4-0-Demethyldiffractaic acid 246
Colensoic acid 316 4-0-Demethylglomellic acid 247
a-Collatolic acid 317 4-0-Demethylglomelliferic acid 247
j3-Collatolic acid 230 4-0 -Demethylglomellin 406
Colour reactions 13-15 4-0-Demethylgrayanic acid 323
13C-NMR spectroscopy 20-22 4-0-Demethylimbricaric acid 247
Concretin 216 Demethylleprapinic acid 400
Condidymic acid 218 4-0-Demethylloxodellic acid 248
Confluentic acid 244 4-0-Demethylmicrophyllinic acid 248
Confumarprotocetraric acid 317 4-0-Demethylnotatic acid 323
Congrayanic acid 231 4-0-Demethylplanaic acid 249
Conhyopoprotocetraric acid 318 2' -0-Demethylpsoromic acid 323
Conloxodin 318 3-0-Demethylscensidin 324
Connorstictic acid 318 3-0-Demethylschizopeltic acid 219
Conorlobaridone 318 4' -0-Demethylsekikaic acid 249
Conphysbdalic acid 319 4-0-Demethylsphaerophorin 249
Conprotocetraric acid 319 4-0-Demethylsquamatic acid 249
Conpsoromic acid 323 4-0-Demethylstenosporic acid 250
Consalazinic acid 319 4-0-Demethylsuperconfluentic acid 250
Constictic acid 320 Depsides 237-312
Constipatic acid 143 Depsidones 313-353
Consuccinprotocetraric acid 320 Depsones 353-356
Contortin 236 Derivatization 109-112
Convirensic acid 320 6a,16fJ-Diacetoxyhopan-22-ol 372
a-Copaene Addenda 3j3,22a-Diacetoxystictane 372
Crustinic acid 303 2a,3j3-Diacetoxystictan -22a-ol 373
Cryptochlorophaeic acid 245 2a,3fJ-Diacetoxystictan-22-one 373
482 Subject Index
2,4-Diacetoxy-3,5,6-trimethylbenzoic acid 407 (- )-Dihydropertusaric acid 144

Diacetyl-12-deoxypyxinol 373 Dihydropicrolichenic acid 265
Diacetylgraciliformin 170 1,8-Dihydroxy-2-chloro-5-methoxy-6-methyl-
Diacetylpyxinol 374 xanthone 197
4,4' -Diacetylscabrosin 128 1,8-Dihydroxy-4-chloro-5-methoxy-6-methyl-
Diacylglyceryltrimethylhomoserines 154 xanthone 197
Diazomethane 109-111 2,6-Dihydroxy-3-chloro-4-methylbenzaldehyde 404
Dibenzofuranes 218-229 2,4-Dihydroxy-5-chloro-6-methylbenzoic acid 406
4,4' -Dibutyrylscabrosin 128 1,7-Dihydroxy-2,4-dichloro-6,8-dimethoxyxantho-
2,4-Dicarboxy-3,5-dimethoxytoluene 407 ne 205
2,4-Dicarboxy-3-hydroxy-5-methoxytoluene 407 2,4-Dihydroxy-3,5-dichloro-6-methylbenzoic
2,4-Dicarboxy-3-methoxy-5-hydroxytoluene 407 acid 409
2,4-Dichloro-3,5-dihydroxytoluene 409 2,4-Dihydroxy-3,5-dichloro-6-n-pentylbenzoic
5,7-Dichloroemodin 171 acid 408
3,5-Dichloroeverninic acid 407 1,8-Dihydroxy-3,6-dimethoxyxanthone 205
2,4-Dichloro-3-hydroxy-5-methoxytoluene 408 2,4-Dihydroxy-3,6-dimethylbenzaldehyde 443
7,7' -Dichlorohypericin 171 2,4-Dihydroxy-3,6-dimethylbenzoic acid 162
3,5-Dichloroisoeverninic acid 408 2,4-Dihydroxy-3,6-dimethyl-5-chlorobenzoic
2,4-Dichlorolichexanthone 197 acid 406
2,5-Dichlorolichexanthone 198 2,4-Dihydroxy-3-formyl- 5-chloro-6-methylbenzoic
2,7 -Dichlorolichexanthone 198 acid 405
4,5-Dichlorolichexanthone 199 2,4-Dihydroxy-3-formyl-6-methylbenzoic acid 425
4,7 -Dichlorolichexanthone 199 2,4-Dihydroxy-5-formyl-6-methylbenzoic acid 427
5,7-Dichlorolichexanthone 199 2,4-Dihydroxy-6-n-heptylbenzene 442
3,5-Dichloro-2' -methylanziaic acid 250 2,4-Dihydroxy-6-n-heptylbenzoic acid 443
2,5-Dichloro-3-0-methylnorlichexanthone 200 6a,22-Dihydroxyhopan-23-oic acid 374
2,5-Dichloro-6-0-methylnorlichexanthone 200 2,6-Dihydroxy-4-hydroxymethylbenzaldehyde 403
2,7 -Dichloro-3-0-methylnorlichexanthone 200 4,6-Dihydroxy-2-methoxy-3-methylacetopheno-
2,7 -Dichloro-6-0-methylnorlichexanthone 201 ne 155
4,5-Dichloro-3-0-methylnorlichexanthone 201 2,5-Dihydroxy-4-methoxy-6-methylbenzaldehy-
4,5-Dichloro-6-0-methylnorlichexanthone 201 de 409
4,7-Dichloro-3-0-methylnorlichexanthone 201 2,5-Dihydroxy-4-methoxy-6-methylbenzoic acid 426
4,7 -Dichloro-6-0-methylnorlichexanthone 202 1,8-Dihydroxy-6-methoxy-3-(3' -oxobut-1' -enyl)-
5,7 -Dichloro-6-0-methylnorlichexanthone 202 anthraquinone 171
2,4-Dichloronorlichexanthone 203 2,3-Dihydroxy-4-methoxy-6-n -propylbenzoic
2,5-Dichloronorlichexanthone 203 acid 425
2,7-Dichloronorlichexanthone 203 2,5-Dihydroxy-3-methoxytoluene 410
4,5-Dichloronorlichexanthone 204 2,4-Dihydroxy-6-methylbenzaldehyde 441
4,7 -Dichloronorlichexanthone 204 2,6-Dihydroxy-4-methylbenzaldehyde 403
5,7 -Dichloronorlichexanthone 205 3,5-Dihydroxy-4-methylbenzoic acid 410
3,5-Dichloroolivetolcarboxyltc acid 408 5,7 -Dihydroxy-6-methylphthalide 156
2,4-Dichloroorcinol 409 2,4-Dihydroxy-6- (2' -oxo-n -heptyl)-benzoic acid 441
3,5-Dichloroorsellinic acid 409 2,4-Dihydroxy-6-n-pentylbenzoic acid 161
Didechlorolecideoidin 324 2,4-Dihydroxy-6-n-propylbenzoic acid 156
Didepsides 237-302 2,4-Dihydroxy-3,5,6-trimethylbenzaldehyde 410
Didymic acid 219 1,3-Dihydroxy-2,4,5-trimethylbenzene 410
l,4-Diethylbenzene 164 2,4-Dihydroxy-3,5,6-trimethylbenzoic acid 440
8',9'-Di-O-ethylsalazinic acid 324 2,4-Dimethoxycarbonyl-3-hydroxy -methoxy-
Diffractaic acid 251 toluene 412
2,4-Diformyl-3,5-dihydroxytoluene 409 2,4-Dimethoxycarbonyl-3 -methoxy-5-hydroxy-
2,6-Diformyl-3,5-dihydroxytoluene 409 toluene 410
Dihydroergosterol 390 2,6-Dimethoxy-3-chloro-4-methylbenzaldehyde 413
Subject Index 483
2,6-Dimethoxy-3-chloro-4-methylbenzoic acid 410 3,5~Dimethylstyrene 164

1,5 -Dimethoxy-4-chloro-6-methyl-8-hydroxy- a,a-Dimethylstyrene 164
xanthone 205 a-p-Dimethylstyrene 164
2,6-Dimethoxy-3,5-dichlorobenzoic acid 411 Dimethylsulfone 131
2,4-Dimethoxy-3,5-dichloro-6-methylbenzoic 2',2" -Di-O-methyltenuiorin 304
acid 413 3,6-Di-O-methylthiophanic acid 206
1,4-Dimethoxy-2,6-dimethylbenzene 411 N,N-Dimethyl-p-toluene sulfonamide 164
2,4-Dimethoxy-3,6-dimethylbenzoic acid 440 4,8-Dimethyltridecane 141
2,4-Dimethoxy-5,6-dimethylbenzoic acid 434 Dinorscensidin 325
2,4-Dimethoxy-6-n-heptylbenzoic acid 411 Diphenylether 229-236
2,4-Dimethoxy-5-hydroxy-6-methylbenzoic acid 414 Diphenylmethanes 236
2,4-Dimethoxy-3-methoxycarbonyl-6-methylbenzoic Diploicin 325
acid 412 Diploschistesic acid 254
2,4-Dimethoxy-6-methylbenzaldehyde 411 4,4' -Disolorinic acid 172
2,4-Dimethoxy-6-methylbenzoic acid 415 Diterpenoids 360-361
2,7 -Dimethoxy-3-methyl-5-hydroxy-6-chloro- Divaric acid 156
anthraquinone 172 Divericatic acid 254
2,4-Dimethoxy-6-(2' -oxo-n -heptyl )-benzoic acid 414 Divaricatinic acid 416
2,4-Dimethoxy-6-(1' -oxo-n-pentyl)-benzoic acid 437 Divarinol 156
2,4-Dimethoxy-6-(3' -oxo-n-pentyl)-benzoic acid 412 Divarinolmonomethylether 157
1,3-Dimethoxy-5-n-pentylbenzene 414 Divaronic acid 326
2,4-Dimethoxy-6-n-pentylbenzoic acid 414 Dodecane 140
3,5-Dimethoxyphenol 412 Dolichorrhizin 367
2,4-Dimethoxy-6-n-propylbenzoic acid 413
2,4-Dimethoxy-3,5,6-trimethylbenzoic acid 412 Echinenone 397
2,2' -Di-O-methylanziaic acid 251 Elatinic acid 254
Di-O-methylchloroatranol 413 jJ-Elemene Addenda
4,2' -Di-O-methylconnorstictic acid 325 Emodic acid 172
4,4' -Di-O-methylcryptochlorophaeic acid 252 Emodin 172
3,5-Dimethyldec-3-en-2-one 141 Emodinaldehyde 173
4,6-Dimethyldec-4-en-3-one 141 Endocrocin 173
Di-0-methyl-3,5-dichloroorsellinic acid 413 Entothein 206
2,4-Di-0-methyldivaric acid 413 Enzyme inhibitory activity 4
2,2' -Di-O-methyldivaricatic acid 252 Epanorin 400
1,2-Dimethyl-3-ethylbenzene 164 Epifriedelinol 375
2,4-Di-0-methylgyrophoric acid 303 Epiphorellic acid I 231
4,2"-Di-O-methylgyrophoric acid 303 Epiphorellic acid II 232
4,5-Di-0-methylhiascic acid 304 Episterol 390
1,2-Dimethyl-3-hydroxy-5-methoxybenzene 413 Ergochrome AA 206
2,4-Di-0-methyl-5-hydroxyorsellinic acid 414 Ergochrome AB 206
2,2' -Di-O-methylimbricaric aci~ 252 Ergosta-7,22-dien-3fJ-ol 390
3,5-Dimethyl-4-methoxyphenol 413 Ergosta-7,24(28)-dien-3fJ-ol 390
1,l-Dimethylnoneicosyl everninate 156 Ergosta-3,5-dien-7 -one 390
2,4'-Di-O-methylnorsekikaic acid 253 Ergosta-4,6,8,11,22-pentaen-3fJ-ol 390
Di-O-methylolivetol 414 Ergosta-5,7 -9(11 ),22-tetraen-3fJ-ol 391
2,4-Di-0-methylolivetolcarboxylic acid 414 Ergosta-5,7,14,22-tetraen-3fJ-ol 391
2,4-Di-0-methylolivetonic acid 414 Ergosta-5,7,9(11)-trien-3fJ-ol 391
2,4-Di-0-methylolivetonide 415 Ergost-5-en-3fJ-ol 391
Di-O-methyl-jJ-orcinolcarboxylic acid 440 Ergosterol 391
2,4-Di-O-methylorsellinic acid 415 Ergosterol-5a,8a-peroxide 392
2,4-Di-0-methylsphaerophorolcarboxylic acid 416 Eriodermin 326
2,2' -Di-O-methylstenosporic acid 253 Erythrin 254
484 Subject Index
meso-Erythritol 131 Ethyl 2,4-di -0-methyl-3-chloroolivetolcarboxy-

Erythroglaucin 173 late 420
Erythroglaucine acid Addenda Ethyl 2,4-di-0-methyl-3-chloroorsellinate 421
Erythrommone 214 Ethyl 2,3-dimethylcyclohexan-4,6-dioncarboxy-
2'" -O-Ethyl-f3-alectoronic acid 232 late 420
Ethyl 3-bromo-5-methylorsellinate 416 Ethyl divarate 421
Ethyl 3-chlorodiverate 416 Ethyl divaricatinate 157
Ethyl 3-chlorodivaricatinate 417 Ethylene 137
Ethyl 3-chloroeverninate 417 Ethyl everninate 157
Ethyl 3-chloro-4-0-methylolivetolcarboxylate 417 Ethyl-5-formyl-f3 -orcinolcarboxylate 421
Ethyl 3-chloro-4-0-methylorsellinate 418 Ethyl haematommate 158
Ethyl 3-chloroolivetolcarboxylate 417 Ethyl 2-hydroxy-3-chloro-4-methoxy-6-methyl-
Ethyl 3-chloroorsellinate 418 benzoate 417
Ethyl 5-chloroorsellinate 418 Ethyl 2-hydroxy-3-chloro-4-methoxy-6-n-pentyl-
24 -Ethylcholestan-3f3-o1 392 benzoate 417
24 -Ethylcholest-7-en-3f3-o1 392 Ethyl 2-hydroxy-3-chloro-4-methoxy-6-n-propyl-
Ethyl 3,5-dichloroolivetolcarboxylate 418 benzoate 417
Ethyl 3,5-dichloroorsellinate 419 Ethyl 5-hydroxyeverninate 422
Ethyl 2,4-dihydroxy-3-bromo-5,6-dimethyl- EthyI2-hydroxy-4-methoxy-6-methylbenzoate 421
benzoate 416 Ethyl 2-hydroxy-4-methoxy-3,5,6-trim ethyl-
Ethyl 2,4-dihydroxy-3-chloro-6-methylbenzoate benzoate 422
418 Ethyl isoeverninate 422
Ethyl 2,4-dihydroxy-5-chloro-6-methylbenzoate Ethyl isohaematommate 422
418 Ethyl 2-methoxy-4-hydroxy-5,6-dimethyl-
Ethyl 2,4-dihydroxy-3-chloro-6-n-pentylbenzoate 422
benzoate 417 Ethyl 2-methoxy-4-hydroxy-5-formyl-6- methyl-
Ethyl 2,4-dihydroxy-3-chloro-6-n-propylbenzoate 423
benzoate 416 Ethyl 2-methoxy-4-hydroxy-6-methylbenzoate 422
Ethyl 2,4-dihydroxy-3,5-dichloro-6-methyl- Ethyl 5-methyl-di-0-methylorsellinate 423
benzoate 419 Ethyl 5-methylisoeverninate 422
Ethyl 2,4-dihydroxy-3,5-dichloro-6-n-pentyl- Ethyl 4-0-methylolivetolcarboxylate 158
benzoate 418 Ethyl 5-methyl-f3-orcinolcarboxylate 423
Ethyl 2,4-dihydroxy-3,6-dimethylbenzoate 423 Ethyl 3-methylorsellinate 423
Ethyl 2,4-dihydroxy-5,6-dimethylbenzoate 423 Ethyl 5-methylorsellinate 423
Ethyl 2,4-dihydroxy-3,6-dimethyl-5-formyl- Ethyl olivetolcarboxylate 424
benzoate 421 Ethyl f3-orcinolcarboxylate 423
EthyI2,4-dihydroxy-5-formyl-6-methylbenzoate 422 Ethyl orsellinate 158
EthyI2,4-dihydroxy-6-n-heptylbenzoate 424 6-Ethyl-6-n -pentyl-pentadecan -4,5,7,8,15-pentol-15-
Ethyl 2,5-dihydroxy-4-methoxy-6-methylben- acetate 137
zoate 422 Ethyl sphaerophorolcarboxylate 424
EthyI2,4-dihydroxy-6-n-nonylbenzoate 419 meta-Ethyltoluene 164
Ethyl 2,4-dihydroxy-6-n-penrylbenzoate 424 Eugenitin 185
EthyI2,4-dihydroxy-6-n-propylbenzoate 421 Eugenitol 185
EthyI2,4-dihydroxy-3,5,6-trimethylbenzoate 419 Eumitrin Al 207
Ethyl 2,4-dimethoxy-3-chloro-6-methylbenzoate 421 Eumitrin Az 207
Ethyl 2,4-dimethoxy-3-chloro-6-n-pentyl- Elfmitrin B 208
benzoate 420 Evernic acid 255
Ethyl 2,4-dimethoxy-3-chloro-6-n -propyl- Evernln 255
benzoate 420 Everinaldehyde 424
Ethyl 2,4-dimethoxy-5,6-dimethylbenzoate 423 Everninic acid 425
EthyI2,4-dimethoxy-3,5,6-trimethylbenzoate 420 Extraction and purification of lichen substances
Ethyl di-0-methyl-3-chlorodivarate 420 11-13
Subject Index 485
Fallacinal 173 Griseoxanthone B 193

Fallacinol 174 Griseoxanthone C 210
Farnesane Addenda j1-Gurjunene Addenda
Fatty acids 154 Gyrophoric acid 304
Fecosterol 392
Fenchol 358 Haemathamnolic acid 257
Fern-9(11)-en-3j1,12a-diol 374 Haematommic acid 158
Fern-9(11)-en-3j1,12j1-diol 375 Haematommone 176
Fern-9(11)-en-3,12-dione 375 Haemophaein 220
Flavoobscurin A 174 Haemoventosin 166
Flavoobscurin Bl 174 (Z)-Heptadeca-1,8-diene 140
Flavoobscurin B2 175 n-Heptadecane 138, 140
Fragilin 175 Heptadecanol 141
Fremontol 393 (Z),(Z)-Heptadeca-1,8,11-triene 140
Friedelan-3j1-o1 375 Heptanoic acid 151
Friedelin 375 Hexadecane 140
D-Fructose 131 Hexadecanol 141
Fukinanolide A 359 Hexa-(a-hydroxyisovalerate) 145
Fulgidin 326 Hiasic acid 305
Fulgoicin 327 Hierridin 159
Fumaric acid 144 High performance liquid chromatography
Fumarprotocetraric acid 327 51, 106-107
Fungisterol 393 History of lichen substances 1-3
Furfuraceic acid 220 IH-NMR spectroscopy 19-20
Furfuric acid Homoheveadride 138
Homosekikaic acid 258
D-Galactose 132 Hopan-7,B,22-diol 376
Galactomannan 132 Hopan-11j1,22-diol Addenda
Galactomannan B 132 Hopan-15a,22-diol 376
O-a- D-Galactopyranosyl-( 1--+6)-0-j1- D-galacto- Hopan-16,B,22-diol 376
pyranosyl-(1--+ l)-D-glyceritol 132 Hopan-6a,7,B,22-triol 377
1-0-j1-D-Galactopyranosyl-D-ribitol 132 Hopenone-B 377
Galapagin 186 Hopen-22(29)-en-3-one 381
Galbinic acid 313 Hop-21,BH-22(29)-en-3-one 377
Gangaleoidin 328 Hydrogenolysis 112
Gas liquid chromatography 107-109 8-Hydroxybarbatic acid 258
Glaucophaeic acid 256 1-Hydroxy-2-chloro-5,8-dimethoxy-6-methyl-
Glomellic acid 256 xanthone 196
Glomelliferic acid 257 1-Hydroxy-4-chloro-5,8-dimethoxy-6-methyl-
Glomelliferonic acid 328 xanthone 196
Glomellin 425 2-Hydroxy-3-chloro-4-methoxy-6-methylbenzoic
Glomellonic acid 329 acid 405
Glucomannan 132 2-Hydroxy-3-chloro-4-methoxy-6-n-pentylbenzoic
1-( O-a- D-Glucopyranosyl)-3S,25R-hexa- acid 405
cosanediol 137 3-Hydroxycolensoic acid 330
3-0-j1-D-Glucopyranosyl-D-mannitol 133 1-Hydroxy-2,4-dichloro-6,8-dimethyl-7-methoxy-
D-Glucose 133 xanthone 208
Glyceryl trilinolate 138 2- Hydro~-3,5-dichloro-4-methoxy-6-methylbenzoic
Graciliformin 175 acid 407
Graphenone 138 8-Hydroxydiffractaic acid 258
Graphisquinone 164 2-Hydroxy-3,6-dimethyl-4-methoxy-5-chlorobenzoic
Grayanic acid 329 acid 406
486 Subject Index
2-Hydroxy-3,6-dimethyl-4-methoxybenzoic acid 442 Hypothallin 128

5-Hydroxy-2,4-di-O-methylorsellinic acid 426 Hypothamnolic acid 260
3-Hydroxydivaricatinic acid 425
5-Hydroxyeverninaldehyde 426 Imbricaric acid 261
5-Hydroxyeverninic acid 426 Indolyl-3-acetic acid 128
2-Hydroxy-3-formyl-4- methoxy-6-methylbenzoic myo-Inositol 133
acid 435 IR spectroscopy 18
3j1-Hydroxyhopan-29-oic acid 377 Isidiophorin 333
5-Hydroxylecanoric acid 259 Islandicin 176
2-Hydroxy-4-methoxy-5-chloro-6-n-propylbenzoic Iso-adiantone 382
acid 405 Isoarthothelin 217
2-Hydroxy-4-methoxy-6-methylbenzaldehyde 424 Isobutylbenzene 164
2-Hydroxy-6-methoxy-4-methylbenzaldehyde 403 Isodidymic acid 221
2-Hydroxy-4-methoxy-6-methylbenzoic acid 425 Iso-divaricatinic acid 427
2-Hydroxy-4-methoxy-6- (2' -oxo-n -heptyl) -benzoic Iso-everninic acid 428
acid 439 Isofulgidin 333
2-Hydroxy-4-methoxy-6-( l' -oxo-n-pentyl) -benzoic Iso-haematommic acid 427
acid 428 Isohyperlatolic acid 261
2-Hydroxy-4-methoxy-6-( 2' -oxo-n -pentyl)-benzoic Isohyperpicrolichenic acid 353
acid 426 Isohyperplanaic acid 262
2-Hydroxy-4-methoxy-6-( 3' -oxo-n -pentyl )-benzoic Isohypocrellin 185
acid 426 Isolecanoric acid 262
2-Hydroxy-4-methoxy-6-n-pentylbenzoic acid 438 Isolichenin 133
2-Hydroxy-4-methoxy-6-n-propylbenzoic acid 416 Isomegapicrolichenic acid 354
3-Hydroxy-5-methoxytoluene 163 Isomerochlorophaeic acid 262
4'-Hydroxy-8-methoxytrypthelone methyl ether 166 Isomultiflorenone 379
3-Hydroxy-5-methyl-4,6-dimethoxy-2- Isomuronic acid 145
(tricos-9' -enyl)-benzene 159 Iso-norlobaridone 233
3j1-Hydroxy-30-nor-hopan-22-one 377 Isonorobtusatic acid 263
3j1-Hydroxyolea-12-en-ll-one 378 Isonotatic acid 333
5-Hydroxy-j1-orcinolcarboxylic acid 426 Isopatagonic acid 263
3-Hydroxyphysodic acid 330 Isopropylbenzene 164
2-Hydroxypulvic acid lactone 400 Isopseudocyphellarin A 263
22a-Hydroxy-3,4-secostict-4(23)-en-3-al 378 Isorangiformic acid 145
22a-Hydroxy-3,4-secostict-4(23)-en-3-oic acid 379 Iso-rhizonic acid 427
22a-Hydroxystictan-3-one 378 Isoschizopeltic acid 221
2-Hydroxy-3,5,6-trimethyl-4-methoxybenzoic Isosphaeric acid 263
acid 427 Isosubpicrolichenic acid 354
3-Hydroxyumbilicaric acid 305 Iso-thujone 359
4-Hydroxyvulpinic acid 400 (+)-and (-)-Isousnic acid 221
Hyperconfluentic acid 259, Isovicanicin 333
Hyperhomosekikaic acid 259
Hyperlatolic acid 259 Jackinic acid 146
Hyperpicrolichenic acid 353 (-)-ent-Kauran-16a-ol 360
Hyperplanaic acid 260
Hypoconstictic acid 331 Key for the identification of lichen substances
Hyponephroarctin 260 122
Hypoprotocetraric acid 331
Hypopsoromic acid 332 Lactone carboxylic acid from Cladonia impexa 146
Hyposalazinic acid 332 Lactone carboxylic acid from Lecanora rupicola 146
Hypostictic acid 332 Lactone of 2,4-dihydroxy-6-(2' -hyd,roxy-n-hept-
Hypostrepsilic acid 220 l' -enyl)-benzoic acid 441
Subject Index 487
Lactone of 2,4-dihydroxy-6-(2'-hydroxy-n-pent- Malonprotocetraric acid 336

l' -enyl)-benzoic acid 406 D-Mannitol 134
Lactone of 2,4-dimethoxy-6-(2'-hydroxy-n-hept- Manool 360
1'-enyl)-benzoic acid 415 Mass spectrometry 22-28
Lactone of 2-hydroxy-4-methoxy-6-(2' -hydroxy- Megapicrolichenic acid 354
n-hept-1'-enyl)-benzoic acid 441 Melacarpic acid 222
Lactone of 2-hydroxy-4-methoxy-6-(2' -hydroxy- Melting point 13, 113-121
n-pent-l'-enyl)-benzoic acid 425 Menegazziaic acid 336
Lactone of 2-methoxy-4-hydroxy-6-(2'-hydroxy- Merochlorophaeic acid 265
n-hept-l'-enyl)-benzoic acid 439 Mesitylene 164
Lanosterol 379 Mesityloxide 141
Laser microprobe mass spectrometry (LAMMA) 1-Methoxy-4-chloro-5,8-dihydroxy-6-methyl-
109 xanthone 209
Lecanoric acid 264 2-Methoxy-3-chloro-6-hydroxybenzoic acid 428
Lecideoidin 334 3-Methoxycolensoic acid 337
Leoidin 334 2-Methoxy-3,5-dichloro-4-hydroxy-6-methylbenzoic
Leprapinic acid 401 acid 408
Leprapinic acid methyl ether 401 2-Methoxy-3,6-dimethyl-4-hydroxybenzal-
Lepraric acid 186 dehyde 428
Leprolomin 233 3-Methoxy-2,4-di-0-methylgyrophoric acid 305
Lepranthin 139 2-Methoxy-3,6-dimethyl-4-hydroxybenzoic acid 427
Lesdainin 366 2-Methoxy-4-hydroxy-5-formyl-6-methylbenzoic
Leucotylic acid 379 acid 428
Leucotylin 380 2-Methoxy-4-hydroxy-6-methylbenzoic acid 427
Lichenin 133 2-Methoxy-4-hydroxy -6-( 2' -oxo-n -heptyl) -benzoic
Lichens as basic material for perfume 5 acid 439
Lichens as biomonitors 6 2-Methoxy-4-hydroxy-6-n-pentylbenzoic acid 438
Lichens as raw material for dyes 5 2-Methoxy-4-hydroxy-6-n-propylbenzoic acid 427
Lichens in folk medicine 4 2-Methoxy-3-methyl-4-hydroxy-5,6-diformylbenzoic
Lichesterinic acid 146 acid 406
Lichesterol 393 Methoxymicareic acid 234
()-Lichesterylic acid 147 3-Methoxy-2,4,5-trimethylphenol 429
Lichexanthone 208 3-Methoxy-2,5,6-trimethylphenol 429
Limonene 358 3-Methoxy-4,5,6-trimethylphenol 429
Linalool 358 8-Methoxytrypthelone methyl ether 167
Linoleic acid 147 3-Methoxyumbilicaric acid 306
Lipids 154 p-Methylacetophenone 164
Lividic acid 334 MethyI3-0-acetylpyxinate 381
Lobaric acid 335 2-0-Methylanziaic acid 265
Lobaritonic acid 428 2' -0-Methylanziaic acid 266
Lobodirin 187 6-0-Methylarthothelin 209
Longifolene Addenda Methyl ascomatate 222
Loxodellic acid 264 3-0-Methylasemone 209
Loxodellonic acid 335 6-0-Methylasemone 210
Loxodin 336 Methylation 109
Loxodinol 234 2'-0-Methylatranorin 266
Lup-20(29)-en-3-one 381 6-0-Methylaverantin 176
Lupeol 380 6-0-Methylaverythrin 176
Lupeone 381 Methyl barbatate 266
Lutein 398 1-0-Methyl-7 -chlorocitreosin 177
Lutein epoxide 398 Methyl 5-chloro-4-0-demethylbarbat;:tte 266
Methyl 3-chloro-di-O-methylorsellinate 429
488 Subject Index
1-0-Methyl-7 -chloroemodin 177 Methyl 2,4-dimethoxy-3-hydroxy-6-n-pentyl-

Methyl 3-chloroeverninate 429 benzoate 434
Methyl 5-chlorohaematommate 430 Methy12,4-dimethoxy-6-methylbenzoate 434
Methyl 5-chloro-iso-everninate 430 Methy13,5-dimethoxy-4-methylbenzoate 433
Methyl-5-chloronorobtusate 267 Methyl 2,2' -di-O-methyleriodermate 269
Methyl 3-chloroorsellinate 430 Methyl 2,4-di-0-methyl-3-hydroxyolivetolcarb-
Methyl 5-chloroorsellinate 430 oxylate 434
Methyl 5-chlorovirensate 345 Methyl di-O-methylorsellinate 434
24 .; -Methylcholestan-3fJ-ol 394 5-Methyl-di-0-methylorsellinic acid 434
2-0-Methylconfluentic acid 267 4-0-Methyldiploicin 338
4-0-Methylcryptochlorophaeic acid 268 Methyl divarate 434
4' -0-Methylcryptochlorophaeic acid 268 2-0-Methyldivaricatic acid 269
2-Methyldecalin 141 2' -O-Methyldivaricatic acid 270
4-0-Methyl-5-dechlorovicanicin 337 2-0-Methyldivaricatinic acid 434
Methyl 4-0-demethylbarbatate 268 Methyl trans-dodec-9-enoate 141
Methyl 3,4-dicarboxy-3-hydroxy-19-oxoeicosa- (- )-2-Methylene-3 (R) -carboxy-18(R) -hydroxynonade-
noate 147 canoic acid 147
Methyl 3,5-dichloroeverninate 431 Methyl eriodermate 270
Methyl 3,5-dichloro-iso-everninate 431 Methyl evernate 270
Methyl 3,5-dichlorolecanorate 269 2'-0-Methylevernic acid 271
Methy15,1'-dichloronorpsoromate 338 3' -0-Methylevernic acid 270
Methyl 3,5-dichloroorsellinate 431 Methyl everninate 434
Methy15,1'-dichloropsoromate 338 1-0-Methylfragilin 177
Methy12,6-dihydroxybenzoate 431 8-0-Methylfragilin 177
Methyl 2,4-dihydroxy-3-chloro-6-methyl- 2-0-Methylglomelliferic acid 271
benzoate 430 Methyl gyrophorate 306
Methyl 2,4-dihydroxy-5-chloro-6-methyl- 4-0-Methylgyrophoric acid 306
benzoate 430 2" -O-Methylgyrophoric acid 307
Methyl 2,6-dihydroxy-3,5-dichlorobenzoate 432 Methyl haematommate 435
Methyl 2,4-dihydroxy-3,5-dichloro-6-methyl- 4-0-Methylhaematommic acid 435
benzoate 431 2-0-Methylhiascic acid 307
Methyl 2,4-dihydroxy-3,6-dimethylbenzoate 160 4-0-Methylhiascic acid 308
Methyl 2,4-dihydroxy-3-formyl- 5-chloro-6-methyl- 5-0-Methylhiascic acid 308
benzoate 430 2' -O-Methylhiascic acid 307
Methyl 2,4-dihydroxy-3-formyl-6- methyl- Methyl 8-hydroxybarbatate 271
benzoate 435 Methyl 2-hydroxy-3-chloro-6-methoxybenzoate 435
Methyl 2,4-dihydroxy-3-methoxy-6-methyl- Methyl 2-hydroxy-3-chloro-4-methoxy-6-methyl-
benzoate 437 benzoate 429
Methyl 2,5-dihydroxy-4-methoxy-6-methyl- Methyl 8-hydroxy-4-0-demethylbarbatate 272
benzoate 436 Methyl 3-hydroxydivarate 436
Methyl 2,4-dihydroxy-6-methylb enzo ate 160 Methyl 5-hydroxyeverninate 436
Methy12,4-dihydroxy-6-n-propylbenzoate 434 Methyl 2-hydroxy-3-formyl-4-methoxy-6-methyl-
Methyl 2,4-dihydroxy-3,5,6-trimethylbenzoate 432 benzoate 438
Methyl 2,6-dimethoxybenzoate 432 Methyl 2-hydroxy-4-methoxy-3,5-dichloro-6-methyl-
Methyl 2,6-dimethoxy-3-chlorobenzoate 432 benzoate 431
Methyl 2,4-dimethoxy-3-chloro-6-methylben- Methyl 2-hydroxy-4-methoxy-6-methylbenzoate 434
zoate 429 Methyl 2-hydroxy-4-methoxy-6-n -pentyl-
Methyl 2,6-dimethoxy-3,5-dichlorobenzoate 433 benzoate 438
Methyl 2,4-dimethoxy-5-formyl-6-methyl- 2-Methy15-hydroxymethyl-7-methoxychromone 187
benzoate 433 Methy13-hydroxyorsellinate 436
Methyl 2,4-dimethoxy-5-hydroxy-6-methyl- Methyl 5-hydroxyorsellinate 436
benzoate 433 9-Methy14-hydroxypannarate 222
Subject Index 489
2-0-Methylhyperlatolic acid 272 4-0-Methylolivetonic acid 439

2' -0-Methylhyperlatolic acid 272 2-0-Methylolivetonide 439
4-0-Methylhyperolivetoric acid 273 4-0-Methylolivetonide 439
2'-0-Methylhyperphyllinic acid 273 4-0-Methylolivetoric acid 281
4-0-Methylhypophysciosporin 338 Methyl ft-orcinolcarboxylate 160
4-0-Methylhypoprotocetraric acid 339 4-0-Methyl-fJ-orcinolcarboxylic acid 442
2'-0-Methylimbricaric acid 274 5-Methyl-fJ-orcinolcarboxylic acid 440
4-0-Methylisocryptochlorophaeic acid 274 Methyl orsellinate 160
Methyl iso-divaricatinate 436 4'-0-Methyl-2"-oxo-cryptochlorophaeic acid 282
Methyl iso-everninate 437 4' -0-Methylpaludosic acid 282
2-0-Methylisohyperlatolic acid 274 9-Methyl pannarate 224
2'-0-Methylisohyperlatolic acid 275 IS-Methyl pannarate 224
2'-0-Methylisopseudocyphellarin A 275 3-0-Methylpannaric acid 224
Methyl iso-rhizonate 437 8-0-Methylpannaric acid 224
Methyllecanorate 275 4-0-Methylpannarin 339
3-0-Methyllividic acid 339 2-Methylpentadecane 140
2-0-Methyllobaritonic acid 437 2-0-Methylperlatolic acid 282
Methyl 2-methoxy-3,5-dichloro-4-hydroxy-6-methyl- 2' -0-Methylperlatolic acid 282
benzoate 431 2'-0-Methylphenarctin 283
Methyl 2-methoxy -3,6-dimethyl-4-hydroxy- 4-0-Methylphysodic acid 340
benzoate 437 2' -0-Methylphysodic acid 340
Methyl 2-methoxy-4-hydroxy-5-chloro-6-methyl- 2' -0-Methylphysodone 234
benzoate 430 Methyl porphyrilate 225
MethyI2-methoxy-4-hydroxy-6-methylbenzoate 437 Methyl protolichesterinate 140
Methyl3-methoxyorsellinate 437 2' -0-Methylpseudocyphellarin A 283
Methyl 2-0-methyleriodermate 276 Methyl pyxinate 381
Methyl 4-0-methyleriodermate 276 2-0-Methylrhizonic acid 440
Methyl 2'-0-methyleriodermate 276 2-0-Methylsekikaic acid 284
Methyl 4-0-methylhaematommate 438 Methyl sekikate 284
Methyl 3' -methyllecanorate 276 2-0-Methylsquamatic acid 284
Methyl 6-0-methylnorascomatate 223 2-0-Methylstenosporic acid 285
Methyl 4-0-methylolivetolcarboxylate 438 2' -0-Methylstenosporic acid 285
9-MethyI8-0-methylpannarate 223 Methylstictic acid 341
2'-0-Methylmicrophyllinic acid 277 2-0-Methylsulphurellin 285
6-0-Methylnorascomatic acid 223 2-0-Methylsuperlatolic acid 286
2'-0-Methylnorbarbatic acid 277 2' -0-Methylsuperlatolic acid 286
4' -0-Methylnorcryptochlorophaeic acid 278 4-0-Methylsuperolivetoric acid 286
2-0-Methylnordivaricatic acid 278 2'-0-Methylsuperphyllinic acid 287
4'-0-Methylnorhomosekikaic acid 278 2-0-Methyltenuiorin 308
2-0-Methylnorimbricaric acid 278 2' -0-Methyltenuiorin 309
3-0-Methylnorlichexanthone 210 2"-0-Methyltenuiorin 309
6-0-Methylnorlichexanthone 210 8-0-Methylthiomelin 210
Methyl norlobarate 336 3-0-Methylthiophanic acid 211
2' -O-Methylnorobtusatic acid 279 6-0-Methylthiophanic acid 211
4'-0-Methylnorsekikaic acid 279 2-Methyltridecane 141
2-0-Methylnorstenosporic acid 280 Methyl 2,3,4-trihydroxy-6-methylbenzoate 436
2-0-Methylnorsuperlatolic acid 280 MethyI2;4,5-trihydroxy-6-methylbenzoate 436
2 -O-Methylnorsuperphyllinic acid 280 Methyl 2,3,4-trihydroxy-6-n-propylbenzoate 436
2-0-Methylobtusatic acid 281 Methyl 2,4,5-trimethoxy-6-methylbenzoate 440
2-0-Methylolivetolcarboxylic acid 438 3-Methylundec-5-ene 141
4-0-Methylolivetolcarboxylic acid 159 4-0-Methylvicanicin 341
2-0-Methylolivetonic acid 439 Methyl virensate 341
490 Subject Index
Micareic acid 235 Nornotatic acid 343

Microcrystallization 47-106 Norobtusatic acid 289
Microphyllinic acid 287 Norpannarin 343
Miriquidic acid 288 Norrangiformic acid 150
Molecular weights and formulae of lichen substances Norsolorinic acid 178
29-46 Norstictic acid 343
Mollin 187 Northiomelin 212
Monoacetylfallacinol 178 Norvicanicin 344
Monoacetylgraciliformin 178 Notatic acid 344
Monocyclic aromatic compounds 155-164 Nostoclides 236-237
Monosaccharides 131-136 Nostoclide I 236
Monoterpenoids 356-359 Nostoclide II 237
(+)-Montagnetol 160
Moretenone 381 Obtusatic acid 290
Murolic acid 148 Oenanthic acid 151
Muronic acid 148 Oleic acid 151
Mutatoxanthin 398 Olivetol 161
a-Muurolene Addenda Olivetolcarboxylic acid 161
Myrcene 358 Olivetolmonomethylether 162
Olivetonic acid 441
NA-3 260 Olivetonide 441
Naphthalene 164 Olivetoric acid 290
Naphthaquinones 164-168 Optical rotation 28
Naphthopyranes 356 Optical rotatory dispersion and circular dichroism
N-containing compounds 126-130 28,47
Nemetzone 178 Orcinol 162
Neodihydromurolic acid 149 fJ-Orcinol 162
Neopsoromic acid 323 Orcinolaldehyde 441
Neoxanthin 398 fJ-Orcinolaldehyde 442
Nephroarctin 288 fJ-Orcinolcarboxylic acid 162
Nephromopsinic acid 149 Orcinoldimethylether 163
Nephrosteranic acid 149 Orcinolmonomethylether 163
Nephrosterinic acid 150 fJ-Orcinolmonomethylether 163
Neuropogolic acid 150 Orcinyl lecanorate 309
Neutral compounds 136-141 Orsellinic acid 163
n-Nonacosan-l0-ol 140 Ovoic acid 309
Nonane 140 Oxostenosporic acid 291
Norargopsin 341 Oxydation 112
Norascomatic acid 225 Oxysiphulin 188
Norcaperatic acid 150 Oxyskyrin 179
Norcolensoic acid 342
Nordechloropannarin 342 Palmitic acid 151
Nordivaricatic acid 288 Paludosic acid 291
Norgangaleoidin 342 Pannaric acid 225
30-Nor-21a-H-hopan-3,22-dione 382 Pannarin 345
30-Nor-21a-H-hopan-22-one 382 Papulosin 179
Norisonotatic acid 342 Parietin 179
Nor-iso-obtusatic acid 289 Parietinic acid 180
Norlichexanthone 211 Patagonic acid 291
Norlobaridone 343 PC-3-glucan 134
Norlobariol 235 P-containing compounds 130
Norlobariolpseudoester 235 Peltigeroside 134
Subject Index 491
Pentadecane 140 C40 -C 130 Polyisoprenoid alcohols 154

Pentadecanoic acid 151 Polyols 131-136
Pentadec-l-ene 140 Polyporic acid 184
1,4,5,6,8-Pentahydroxy-3-methylanthraquinone 180 Poriferasterol 394
Perlatolic acid 292 Porphyrilic acid 226
5a,8a-Peroxyergosteryl divaricatinate 394 Portentol 140
Perylenequinones 185 Prasinic acid 293
Phenacyl esters 111 Praesorediosic acid 151
Phenanthrenequinones 184 Protocetraric acid 347
Phenarctin 292 Protoconstipatic acid 152
Phenol 164 Protolichesterinic acid 152
2-Phenyldecane 164 Protopraesorediosic acid 152
4-Phenyldecane 164 Protosiphulin 188
5-Phenyldecane 164 Prunastric acid 294
I-Phenyldec-3-ene 164 Pseudocyphellarin A 294
2-Phenyldodecane 164 Pseudocyphellarin B 295
3-Phenyldodecane 164 Pseudonorrangiformic acid 153
4-Phenyldodecane 164 (-) -Pseudoplacodiolic acid 226
5-Phenyldodecane 164 Psoromic acid 347
5-Phenyldodec-3-ene 164 Pulvic acid lactone 402
2-Phenyltridecane 164 Pulvinamide 402
4-Phenyltridecane 164 Pulvinic acid 402
5-Phenyltridecane 164 Pulvinic acid derivatives 399-403
2-Phenylundecane 164 Pustulan 134
3-Phenylundecane 164 Pyxinic acid 384
4-Phenylundecane 164 Pyxinol 384
5-Phenylundecane 164
5-Phenylundec-3-ene 164 Ramalinaic acid 295
Phlebic acid A 382 Ramalinolic acid 295
Phlebic acid B 383 Rangiformic acid 153
Phlebic acid C 383 Retigeradiol 385
Phlebic acid D 383 Retigeranic acid A 361
Phloroglucinoltrimethylether 442 Retigeranic acid B 361
Phosphatidylcholine 130 Retigeric acid A 384
Phosphatidylethanolamine 130 Retigeric acid B 384
Phosphatidylglycerol 130 Rhizocarpic acid 402
Phospholipides 154 Rhizonic acid 442
Phthalic acid 164 Rhodoc1adonic acid 167
Phyllopsorin 345 Ribitol 135
Physcion 179 Rimuene 360
Physciosporin 345 Roccanin 129
Physodalic acid 346 Roccellaric acid 153
Physodic acid 345 Roccellic acid 154
Phytol 360 Roccellin 188
Picrolichenic acid 355 Rugulosin 180
Picroroccellin 129 Russulone 181
Pinastric acid 401
a-Pinene 358 Salazinic acid 348
,B-Pinene 358 (-)-Sandaracopimaric acid 361
(-) -Placodiolic acid 226 Sativic acid 154
Planaic acid 293 Scensidin 348
Plant growth inhibitory activity 4 Schizopeltic acid 227
492 Subject Index
Schottenol 395 Succinprotocetraric acid 350

meta-Scrobiculin 296 Sucrose 135
para-Scrobiculin 296 Superconfluentic acid 300
S-containing compounds 131 Superlatolic acid 293
Secalonic acid A 206 Superpicrolichenic acid 356
Secalonic acid C 206 Superplanaic acid 300
Sekikaic acid 296
j3-Selinene Addenda D-Tagatose 135
Sesquiterpenoids 359 Taraxaxanthin 398
Sesterterpenoids 361 Taraxer-14-ene 385
Simonyellin 356 Taraxerol 386
Siphulellic acid 348 Taraxerone 386
Siphulin 189 Taurine 130
Siphulitol 135 Teloschistin 174
j3-Sitosterol 394 Tenuiorin 310
SJ-2-I-glucan 135 Terpenoids 356-399
Skyrin 181 Terphenylquinones 184
Skyrinol 181 Terpinen-4-ol 359
(+ )-Sodium usneate 227 a-Terpineol 359
Solorinic acid 182 Tert-butyI5-chlorohaematommate 443
Solorinin 129 Tert-butyl 2,4-dihydroxy-3,6-dimethylbenzoate 445
Sordidone 189 Tert-butyl 2,4-dihydroxy-3-formyl- 5-chloro-6-methyl-
Sphaerophorin 297 benzoate 443
Sphaerophorol 442 Tert-butyI2,4-dihydroxy-6-methylbenzoate 445
Sphaerophorolcarboxylic acid 443 Tert-butyl everninate 443
Squamarone Addenda Tert-butyl haematommate 444
Squamatic acid 297 Tert-butyl 2-hydroxy-3,6-dimethyl-4-methoxyben-
Stearic acid 154 zoate 445
Stenosporic acid 298 Tert -butyl 2-hydroxy-4-methoxy-6-methylben-
Stenosporonic acid 349 zoate 443
Steroids 388-396 Tert-butyl 2-hydroxy-4-methoxy-6-(2' -oxo-n-heptyl)-
Stictan-3j3,22a-diol 385 benzoate 444
Stictan-2a,3j3,22a-triol 385 Tert-butyl 2-hydroxy-4-methoxy-6-n -pentyl-
Stictic acid 349 benzoate 444
Sticticin 129 Tert-butyl 4-0-methylolivetolcarboxylic acid 444
Stigmasta-3,5-dien-7-one 395 Tert-buty14-0-methylolivetonate 444
Stigmasta-3,5,22-trien-7 -one 395 Tert-butyl j3-orcinolcarboxylate 445
Stigmast-7-en-3j3-ol 395 Tert-butyl orsellinate 164
Stigmast-4-en-3-one 395 ortho-Tert-butylphenol 164
Stigmasterol 395 Tert-butyl rhizonate 445
Strepsilin 227 2,2' -7,7' -Tetrachlorohypericin 182
Subconfluentic acid 298 Tetradecane 140
Subdidymic acid 228 Tetradec-1-ene 141
Subdivaricatic acid 299 Tetradepsides 302
Submerochlorophaeic acid 299 1,4,5,8-Tetrahydroxy-3-ethylnaphtho-2,6-
Subnotatic acid 350 quinone 167
Subpaludosic acid 299 2,5,6,8-Tetrahydroxy-3-ethylnaphtho-1,4-
Subpicrolichenic acid 355 quinone 167
Subsekikaic acid 300 Tetrahydroxyfattyacids 154
Subsphaeric acid 300 1,5,6,8-Tetrahydroxy-3-methylanthraquinone 182
Substictic acid 350 3,6,3' ,6' -Tetrahydroxy-4-methylbiphenyl-2,5,2',5'-
Succinic acid 443 diquinone 183
Subject Index 493
9,lO,12,13-Tetrahydroxystearic acid 154 3,4,5-Trihydroxytoluene 446

Thamnol 445 1,5,8-Trimethoxy-2-chloro-6-methylxanthone 217
Thamnolic acid 301 Tri-0-methylarthothelin 217
Thelephoric acid 184 1,2,3-Trimethylbenzene 164
Thin layer chromatography 47, 51 2,4,5-Tri-O-methylhiascic acid 3 lO
Thiomelin 212 2,5,6-Trimethyl-3-methoxyphenol 446
Thiophanic acid 212 2,4,6-Trimethylorcinol 446
Thiophaninic acid 213 Triterpenoids 362-388
a- Thujone 359 Trypethelone 168
/3- Thujone 359 Trypethelone methyl ether 168
Thujopsene Addenda Tumidulin 269
Thuringione 213
Thymol 164 Umbilicaric acid 311
Toluene 164 Umbilicin 136
Trehalose 135 Undecane 140
2a,3/3,22a- Triacetoxystictane 386 Ursolic acid 386
2,4,5-Trichloro-3,6-di-0-acetylnorlichexanthone 214 (+ )-and (-)-Usnic acid 228
2,4,5-Trichlorolichexanthone 214 UV-spectroscopy 15-18
2,4,7 -Trichlorolichexanthone 214
2,5,7 -Trichlorolichexanthone 215
Valsarin 179
4,5,7 -Trichlorolichexanthone 215 Variolaric acid 351
2,4,7 -Trichloro-3 -0-methylnorlichexanthone 215
Vesuvianic acid 351
2,4,7 -Trichloro-6-0-methylnorlichexanthone 215 Vicanicin 352
2,5,7-Trichloro-3-0-methylnorlichexanthone 216 Vinetorin 217
2,5,7 -Trichloro-6-0-methylnorlichexanthone 216 Violaxanthin 399
4,5,7 -Trichloro-3-0-methylnorlichexanthone 209 Virensic acid . 352
4,5,7 -Trichloro-6-0-methylnorlichexanthone 210
Vittatolic acid 352
2,4,5-Trichloronorlichexanthone 216 Volemitol 136
2,4,7 -Trichloronorlichexanthone 216
Vulpinic acid 403
Tridecane 140 WINTABOLITES 107
Tridepsides 302-311 Wrightiin 301
1,5,8-Trihydroxy-2,4-dichloro-6-methylxanthone
212 Xantholamine 130
2,4,5-Trihydroxy-3,6-dimethylbenzoic acid 426 Xanthones 190-218
2,5,7 -Trihydroxyemodin 183 Xanthorin 183
2,3,6-Trihydroxy-4-methylbenzaldehyde 445 X-ray analysis lO9-110
1,6,8-Trihydroxy-3-methyl-7 -chloro-l O-anthrone
183 Zeaxanthin 399
1,6,8-Trihydroxy-3-methyl-5,7 -dichloro-9- Zeorin 387
anthrone Addenda Zeorinone 387

Identification of Lichen Substances (Huneck & Yoshimura 1996)

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Identification of Lichen Substances (Huneck & Yoshimura 1996)

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Siegfried Huneck and Isao Yoshimura

Identification of Lichen Substances

Professor Dr. ISAo YOSHIMURA

Library of Congress Cataloging-in-Publication Data

Huneck, S. (Siegfried), 1928-

Springer-Verlag Berlin Heidelberg ~996

Typesetting: Best-set Typesetters Ltd., Hong Kong

1.1 Short History of the Study of Lichen Substances. . . . . . . . 1

2 Identification of Lichen Substances. . . . . . . . . . . . . . . . . . 11

2.1 Extraction and Purification of Lichen Substances. . . . . . . 11

2.9 Optical Rotatory Dispersion (ORD) and

3 Data of Lichen Substances ......................... . 125

3.18 Depsones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

Addenda .............................................. 475

Subject Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479

1.1 Saxony, Germany, died 1917 at Feuerbach near

Fig. 2. Y. Asahina Fig. 3. S. Shibata

usnic acid (Kupchan and Kopperman 1975; methylcryptochlorophaeic acid (prostaglan-

expected that the coming years will bring new 1.2.4

Lichen Lichen substances from:

Intact lichen Mycobiont Lichen culture Literature

Anaptychia hypoleuca Atranorin + Ejiri and Shibata (1974)

Lichen Lichen substances from:

Intact lichen Mycobiont Lichen culture Literature

Lecanora rupicola Atranorin Eugenitin Fox and Huneck (1969)

- - - - electric water bath

solvent, e.g. acetone or chloroform, silica gel

Alectorialic acid 2,5-Dichloronorlichexanthone 2'-0-Methylnorsuperphyllinic acid

R-CHO + P-H2N-C6 H4-NH2 ~ A similar diagnostic colour reagent,

a-Acetylconstictic acid 2'-0-Demethylpsoromic acid Norargopsin

Allorhizin methylnorlichexanthone Methyl 5-chloronorobtusate

d (logE 3.75). Depsidones with an aldehyde group

Table 5. UV data of 15 selected depsides

Depside Amax. nm (loge)

Atranorin 210 (4.20) 252 (4.16) 312 (3.57)

Table 6. UV data of nine selected depsidones

Depsidone A.max' nm (logE)

Colensoic acid 256 (4.2) 310 (3.3)

Table 7. UV data of o:-methylene-y-lactones and o:,~

with a hydroxyl group in p-position to the car- 2.5

Table 8. UV data of 11 lichen quinones

Quinone Amax' nm (logE)

2.6 Overhauser Effect) difference spectra; this is an

Fig.6. lH-NMR spectrum (200 MHz, CDCl3 ) of methyl glomellate

Table 10. 13C-NMR shifts of groups present in lichens

2.7 Wilkins (1979) studied the MS of di- and tri-

1.0 M (+)-usnic acid in CDCl3

Table 11. Mass spectrometric fragments of lichen depsides

m/z Formula Structure mlz Formula Structure

150 CaH6 O, Me-

Table 11. Continued

mlz Formula Structure mlz Formula Structure

Table 11. Continued

m/z Formula Structure m/z Formula Structure

CI3 H l6 0 3 C5 H" ~~ ~CO'

248 Cl4Hl604 C5 H"

Table 11. Continued The formula of an organic compound can

II II, III, III ,

Table 12. Molecular weights and formulae of lichen substances