Biochemical Systematics and Ecology 28 (2000) 351}366

The distribution of iridoids in Bignoniaceae

Gilsane Lino von Poser!,*, Jan Schripsema",
AmeH lia T. Henriques!, Soren Rosendal Jensen#
!Curso de Po& s-Graduac7 aJ o em CieL ncias FarmaceL uticas, UFRGS, Av. Ipiranga, 2752, 90.610-000,
Porto Alegre, Brazil
"Nu& cleo de Pesquisas de Produtos Naturais, UFRJ, Centro de CieL ncias da Sau& de, Bloco H, 21941-590 - Ilha do
FundaJ o, Rio de Janeiro, Brazil
#Department of Organic Chemistry, The Technical University of Denmark, DK-2800, Lyngby, Denmark
Received 18 February 1999; accepted 11 June 1999

Abstract

The distribution of iridoids among the tribes of Bignoniaceae is shown. In the present work,
18 species from the tribes Bignonieae and Tecomeae as well as one from Eccremocarpeae have
been investigated. These data combined with those obtained through a literature review were
analysed and showed that iridoids occur predominantly in the tribe Tecomeae. In this tribe,
a chemical distintion between the genera Tabebuia and Tecoma was observed: The iridoids in
Tabebuia are decarboxylated whereas in Tecoma they are C-4 formylated. The species from
Bignonieae are poorly investigated and only few reports have been published, however, the
iridoids found are mainly C-4 carboxylated. The only exception, Dolichandra cynanchoides
("Macfadyena cynanchoides), with decarboxylated iridoids, is also morphologically abnormal
in Bignonieae. ( 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Bignoniaceae; Iridoids; Tecomeae; Bignonieae; Chemotaxonomy

1. Introduction

The family Bignoniaceae, order Lamiales (sensu Dahlgren, 1989), consists of about
120 genera and 800 species. The family is largely found in tropical regions of
South America and Africa (Gentry, 1980) but some species are widely cultivated as
ornamentals.

* Corresponding author.
E-mail address: [email protected] (G. Lino von Poser)

0305-1978/00/$ - see front matter ( 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 3 0 5 - 1 9 7 8 ( 9 9 ) 0 0 0 7 6 - 9
352 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

In recent systematic studies, the Bignoniaceae are divided into eight tribes:
Tecomeae, Bignonieae, Crescentieae, Eccremocarpeae, Tourrettieae, Oroxyleae,
Coleeae and Schlegelieae (Gentry, 1980). The last one, which is a small tribe with only
three genera, is regarded as transitional to Scrophulariaceae. Earlier authors only
recognized the "rst "ve tribes (Sandwith and Hunt, 1974).
Of the eight tribes only the "rst three occur in Brazil. They are most easily
distinguished by their habit and fruit structure. Usually, Tecomeae has fruits dehiscent
perpendicular to the septum, and an arborescent habit. Bignonieae has fruits dehis-
cent parallel to the septum and all species are vines. Crescentieae has indehiscent
fruits, as in the calabash-tree, and the species are trees or shrubs (Sandwith and Hunt,
1974; Cronquist, 1981; Barroso, 1986).
Although Bignoniaceae are a relatively large family only a limited number of
species has been studied chemically. In an early work on the distribution of iridoid
 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366 353

glucosides, Hegnauer and Kooiman (1978) studied 48 species from 32 genera, of which
about half the number were positive for iridoids. The detection method was
chromatography and mainly seeds were investigated. In a taxonomic work, Nicoletti
et al. (1984) "nd some consistency in the distribution of some iridoid groups in
di!erent tribes. Thus, they "nd that (i) catalpol (1) derivatives are general within the
tribe Tecomeae, (ii) that aucubin (2) derivatives are restricted to South American
species of Tecomeae, while (iii) aldehydic (3) iridoids are restricted to species from
Africa or from temperate regions. Finally, (iv) they "nd in an investigation of Brazilian
taxa, that species from the semiarid zone usually lack iridoids. Later, Garbarino and
Nicoletti in a work mainly concerning Chilean taxa (1989) stated that the occurrence
of iridoids within the family apparently was restricted to the tribes Tecomeae and
Eccremocarpeae, ignoring or considering unimportant the previously reported isola-
tion of 1 and 2 from Crescentia sp. (Crescentieae) (Hegnauer and Kooiman, 1978) as
well as the isolation of other iridoids from the tribe Bignonieae (Bonini et al., 1981;
Adriani et al., 1982; Krebs, 1987).
To further utilize iridoid glucosides as chemosystematic characters for and within
the family Bignoniaceae, 18 Brazilian and one Chilean species have been investigated.
They constitute 13 species from the tribe Bignonieae, "ve from the Tecomeae and one
from Eccremocarpeae. The results are compared with data from previous chemical
investigations. In the present work, we have not included the monoterpenoid alkal-
oids most of which biosynthetically are of iridoid origin (Cordell, 1977) and which
often are artefacts formed from iridoid aglucones and ammonia during isolation.

2. Material and methods

2.1. General procedures

Prep. TLC was performed on 20]40 cm plates coated with 1mm layers of silicagel
PF (Merck). Reversed phase MPLC was performed on a Merck Lobar C-18
254
column, size C. H O: MeOH mixtures were used as eluents and peaks were detected
2
by UV at 206 and 254 nm. Isolated compounds were identi"ed by their 1H and
13C NMR spectra recorded in D O at 250 and 62.5 MHz, respectively.
2
2.2. Plant material

The plants were collected in the `Morro Santanaa and in the Botanical Garden of
the &Fundac7 a8 o de Zoobota( nica da Secretaria da Agricultura do Estado do Rio
Grande do Sul', Porto Alegre, in August, 1995. The voucher specimens are deposited
in the herbarium of the Federal University of Rio Grande do Sul (ICN) (Jacaranda
micrantha, Sobral 8309; J. puberula, Sobral 8295; Tabebuia alba, Sobral 8299;
T. heptaphylla, Sobral 8296; T. chrysotricha, Sobral 8300; Adenocalymna marginatum,
Sobral 8306; Amphilophium vauthieri, Sobral 8312; Anemopaegna chamberlaynii, Sob-
ral 8297; Arrabidaea chica, Sobral 8301; A. mutabilis, Sobral 8304; A. selloi, Sobral
8305; Clytostoma callistegioides, Sobral 8298; Cuspidaria pterocarpa, Sobral 8310;
354 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

Macfadyena unguis-cati, Sobral 8307; Pyrostegia venusta, Sobral 8302; Pithecoctenium

crucigerum, Sobral 8308; Tynnanthus elegans, Sobral 8311; Urbanolophium dusenianum,
Sobral 8303). Eccremocarpus scaber (voucher IOK-1-89) was cultivated in a green-
house at The Arboretum, Hoersholm, Denmark.

2.3. Extraction of glucosides

The plant material was extracted with EtOH for 4}6 days. The concentrated extract
was partitioned in Et O}H O and the aqueous solutions were concentrated to
2 2
dryness. Prior to the isolation the extracts were analysed for iridoids by TLC using as
eluent CHCl : MeOH (80 : 20) and sulphuric vanillin and heating as chromogenic
3
agent. Some negative results were con"rmed by 1H NMR of the crude extract.

2.4. Isolation of glucosides

2.4.1. Tabebuia heptaphylla

The aqueous solution of the crude extract (1.8 g obtained from 87 g of leaves) was
passed through a layer of Al O (to remove the o-diphenolic compounds) and eluted
2 3
with water (Jensen and Nielsen, 1989). Chromatography on a Silicagel column with
chloroform}methanol mixtures as eluent and subsequent puri"cation by preparative
TLC gave 6-O-p-hydroxybenzoyl-6-epi-aucubin (4; 70 mg) (Bianco et al., 1982c).

2.4.2. Pithecoctenium crucigerum

The concentrated aqueous phase (2.98 g from 103 g of leaves), was chromatog-
raphed on an RP C-column eluting with H O : MeOH (25 : 1 to 1 : 1), gave "rst
2
a polar fraction which was discarded. The next fractions were strictoloside (7;80 mg)
(Junior, 1985), theviridoside (5;180 mg) (von Poser et al., 1995) and ipolamiide
(6;100 mg) (Damtoft et al., 1984).

2.4.3. Adenocalymna marginatum

Leaves (68 g) worked-up as described above a!orded 4.05 g of crude extract.
Chromatography on a C-column gave chlorogenic acid (51 mg) (Hennessy et al.,
1989), strictoloside (7;240 mg), theviridoside (5;120 mg) and ipolamiide (6;140 mg).

2.4.4. Eccremocarpus scaber

Fresh foliage (320 g) gave a crude aqueous extract which was treated with Al O to
2 3
give crude glycosides (6.45 g). RP-chromatography as above gave catalpol (1;1.07 g)
(Davini et al., 1983) and cornoside (30 mg) (Kuwajima et al., 1993), followed by
gardoside methylester (10;10 mg) (Bianco et al., 1985) and mussaenoside (11;50 mg)
(Garbarino and Nicoletti, 1989).

3. Results and discussion

The results of our investigation are reported in Table 1 together with the iridoids
reported in the literature for species from Bignoniaceae. Within the family, it seems
 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366 355

that the iridoids are most common in species from the tribe Tecomeae. Conversely, in
the tribe Bignonieae, no iridoids were found in the majority of the investigated species,
at least not in concentrations detectable with the methods used.
In Tecomeae, two of the species investigated, Jacaranda micrantha and J. puberula,
apparently were devoid of iridoids, while the three species of Tabebuia, namely T. alba,
T. heptaphylla and T. chrysotricha all contained the compound 6-O-p-hydroxyben-
zoyl-6-epi-aucubin (4). In earlier studies the analogue iridoid glucoside 5-hydroxy-6-
epi-aucubin ("6-epi-monomelittoside) and some of its benzoyl derivatives have been
reported from the leaves of Tabebuia heptaphylla (Bianco et al., 1983b,c, synonym:
Tecoma heptaphylla). From the bark three benzoyl esters of ajugol were found by
Nakano et al. (1993) synonym: Tabebuia avellanedae). 6-Epi-aucubin (16), 4 and
6-O-foliamenthoyl-6-epi-aucubin ("amarelioside) were isolated from Tabebuia
chrysantha (Bianco et al., 1982a, b and c, synonym: Tecoma chrysantha). Hegnauer and
Kooiman (1978) reported the presence of 1 in Tabebuia serratifolia (synonym: Tecoma
speciosa). As stated above, 4 is present also in Tabebuia alba and Tabebuia chrysot-
richa. The two genera Tecoma and Tabebuia are di$cult to separate taxonomically,
and according to the original reports a number of Tecoma species should contain C-4
decarboxylated iridoids, but after the revision of Gentry (1992), all of these have been
transferred to Tabebuia. Thus, this re-classi"cation is fully supported by the chemical
data which show that C-4 decarboxylated iridoids only occur in Tabebuia, while
Tecoma contains C-4 formyl iridoids.
Iridoids were found in only two of the 13 investigated species within tribe Bi-
gnonieae (Table 1). Remarkably, the compounds theviridoside (5), ipolamiide (6) and
strictoloside (7) were isolated from both the positive species Adenocalymna marginatum
and Pithecoctenium crucigerum. The present work in part con"rms the early results by
Hegnauer and Kooiman (1978) since a species each of Clytostoma and Cuspidaria were
reported to be negative, while one of Pithecoctenium was found to contain `some
iridoids.a Theviridoside (5) has previously been isolated from several sources, namely
from Thevetia peruviana and Cerbera sp. (Apocynaceae) (El-Naggar and Beal, 1980),
from the roots of several species of Lippia and Lantana (Rimpler and Sauerbier, 1986;
von Poser et al., 1997) and from the leaves of Verbenoxylum reitzii (von Poser et al.,
1995) but not so far from Bignoniaceae. Strictoloside (7) has earlier only been reported
from the leaves of Penstemon strictus (Scrophulariaceae) (Junior, 1985). However, this
carboxylated iridoid glucoside with an exocyclic double bond at C-8 is biosyntheti-
cally related to 7-deoxygardoside (8), known from Argylia radiata (Table 1). Ipolami-
ide (6), another C-4-carboxylated iridoid, is common in Lamiales and it is the
biosynthetic precursor for lamiide (9), which is known from Pseudocalymma elegans
(Table 1).
One species from Eccremocarpeae, namely Eccremocarpus scaber was investigated
in the present work to give the iridoid glucosides catalpol (1), gardoside methylester
(10) and mussaenoside (11). Previous work by Garbarino and Nicoletti (1989); see
Table 1) gave mussaenoside as the only iridoid glucoside accompagnied by the
monoterpenes eccremocarpol A (12) and B (13). Catalpol was apparently not detected
by Garbarini and Nicoletti, but 12 and 13 could easily be artefacts derived from
hydrolysed catalpol in aqueous methanol in analogy to specionin (14) which probably
Table 1 356
Species of Bignoniaceae investigated for iridoid glucosides, the compounds reported and their structural type. The names of some species have been revised
(Gentry, 1980,1992) and these are used in the table (the names used in the original publication are presented in footnotes.)
Tribe/species Tecomeae Iridoids Type! References
Amphicome emodi Lindl. Picroside II("amphicoside I) D Kapoor et al. (1971)

Argylia radiata (L.) D. Don Argylioside CD Bianco et al. (1986a)

Catalpol (1) D
Plantarenaloside F
8-epi-7-deoxyloganic acid C
7-deoxygardoside C
Radiatoside CD Bianco et al. (1986b)
Geniposidic acid C Bianco et al. (1987a)
Mussaenosidic acid C
Radiatoside B CD
Radiatoside C CD
Radiatoside D CD Bianco et al. (1991)
Radiatoside E CD Bianco et al. (1992)
Radiatoside F CD
Asthianthus viminalis (H.B.K.) Baillon 5-OH-campenoside F Alvarez et al. (1994)
Campenoside F
Campsidium valdivianum (Phil.) Skotts. Plantarenaloside F Garbarino et al. (1985)
Stansioside F
Plantarenalosigenin-1-O-b- gentiobioside F Bianco et al. (1987b)
Stansiosigenin-1-O-b- gentiobioside F
Campsis chinensis Voss. Campenoside F Kobayashi et al. (1981)
5-OH-campenoside F
Tecomoside F Imakura et al. (1984)
Cachineside I F
Campsiside F Imakura et al. (1985)
Pondraneoside F
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

Cachineside III F Imakura and Kobayashi (1986)

Cachineside IV F
Cachineside V F
Catalpa bignonioides Walt. Catalpol (1) D Plouvier and Favre-Bonvin (1971)
Catalposide (15) D Iwagawa et al. (1991)
 Amphicoside D
Minecoside D
6-O-veratroyl catalpol D
6'-O-p-hydroxybenzoyl catalpol D
6-O-p-hydroxybenzoyl-10-Descinn- D
amoylglobularimine
6-O-p-hydroxybenzoyl-5,7-bisdeoxycynanchoside D
6-O-p-hydroxybenzoyl-7a-hydroxy- D
dechloroglutinoside
5b-hydroxy-6'-O-p-hydroxybenzoyl- D
eucommioside II
Veronicoside D Maksudov et al. (1995b)

C. ovata G. Don Catalposide (15) D Lunn et al. (1962)

C. speciosa Warder Catalposide (15) D El-Naggar and Doskotch (1980)

Specioside D

Catophractes sp. Aucubin (2) D Hegnauer and Kooiman (1978)

Catalpol (1) D

Chilopsis linearis (Cavanilles) Sweet" Catalpol (1) D Hegnauer and Kooiman, 1978
`Catalpolestera D

Cybistax antisyphilitica (Mart.) Mart. Specioside D Felicio et al. (1994)

Macfadienoside D

Deplanchea speciosa Vieill. Plantarenaloside F Davioud et al. (1989)

Dolichandrone sp. Neg. Hegnauer and Kooiman (1978)
Heterophagma sp. Neg. Hegnauer and Kooiman (1978)
Incarvillea olgae Regel Stansioside F Maksudov et al. (1995a)
7-O-benzoyltecomoside F
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

Jacaranda micrantha Cham. Neg. This work

J. puberula Cham. Neg. This work

Markhamia sp. Unidenti"ed ? Hegnauer and Kooiman (1978)

357

*continued
Table 1*continued 358

Tribe/species Tecomeae Iridoids Type! References

Newbouldia sp. Neg. Hegnauer and Kooiman (1978)

Pandorea sp. Neg. Hegnauer and Kooiman (1978)

Paulownia tomentosa (Thunb.) Steud. 7-OH-tomentoside D Damtoft and Jensen (1993)

Catalpol (1) D
Tomentoside D
Aucubin (2) D Adriani et al. (1981)
Paulownioside D

P. coreana Uyeki Catalpol (1) D Damtoft and Jensen (1993)

7-OH-tomentoside D

Podranea ricasoliana Sprague# Pondraneoside F Guiso (1982)

Radermachera sinica Hemsl. Amphicoside D Iwagawa et al. (1990)
Minecoside D
Nemoroside D
Specioside D
6-O-vanilloyl-ajugol D
6-O-octadienoyl-catalpol D
Rhigosum sp. Aucubin (2) D Hegnauer and Kooiman (1978)
Catalpol (1) D

Spathodea campanulata Beauvois Verminoside D Niyonzima et al. (1991)

S. sp. Catalpol (1) D Hegnauer and Kooiman (1978)
Stereospermum personatum (Hassam) Chatterjee Specioside D De Silva et al. (1982)
Tabebuia alba (Cham.) Sandw. 6-O-p-OH-benzoyl-6-epi-aucubin (4) D This work
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

T. chrysantha (Jacq.) Nichols$ 6-epi-aucubin (16) D Bianco et al. (1982a)

Amareloside D Bianco et al. (1982b)
6-O-p-OH-benzoyl-6-epi-aucubin (4) D Bianco et al. (1982c)
T. chrysotricha (Mart. ex DC.) Standley 6-O-p-OH-benzoyl-6-epi-aucubin (4) D This work
T. heptaphylla (Velloso) Toledo% 6-epi-monomelittoside D Bianco et al. (1983b)

6-O-p-OH-benzoyl-epi-monomelittoside D Bianco et al. (1983c)

6-O-p-methoxy-benzoyl-epi-monomelittoside D
6-O-p-OH-benzoyl-ajugol D Nakano et al. (1993)
6-O-p-methoxybenzoyl-ajugol D
6-O-3,4-dimethoxybenzoyl-ajugol D
6-O-p-OH-benzoyl-6-epi-aucubin (4) D This work
T. heterophylla (DC.) Britton& Specioside D Bishay et al. (1987)

T. rosea (Bertol.) DC. Specioside D Compadre et al. (1982)

T. serratifolia (Vahl) Nichols.' Catalpol (1) D Hegnauer and Kooiman (1978)

Tecoma capensis (Thunb.) Lindl. Tecomoside F Bianco et al. (1975)

7-O-cinnamoyl tecomoside F Bianco et al. (1983a)
7-O-coumaroyl tecomoside F
7-O-p-methoxycinnamoyl tecomoside F
7-O-p-OH-benzoyl tecomoside F
7-O-p-methoxy-benzoyl tecomoside F Guiso et al. (197)
T. fulva (Cav.) G. Don Plantarenaloside F Garbarino et al. (1985)
Stansioside F
T. stans Juss. 5-deoxystansioside (5) F Bianco et al. (1981)
Plantarenaloside F Bianco et al. (1982d)
Stansioside F

Tecomaria sp. Neg. Hegnauer and Kooiman (1978)

Tecomella undulata (G. Don) Seem. 6-O-veratrylcatalposide D Joshi et al. (1975)

Tecoside D Verma et al. (1979)
Undulatin D Verma et al. (1986)
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

Bignonieae
Adenocalymna marginatum (Cham.) DC. Ipolamiide (6) C This work
Strictoloside (7) C
Theviridoside (5) C
359

*continued
Table 1*continued 360

Tribe/species Tecomeae Iridoids Type! References

Amphilophium vauthieri DC. Neg. This work

Anemopaegma chamberlaynii (Sims) Bur. Neg. This work

and K. Schum.

Arrabidaea chica (H. and B.) Velot Neg. This work

A. mutabilis Bur. and K. Schum. Neg. This work

A. selloi (Spreng.) Sandw. Neg. This work
Bignonia sp. Neg. Hegnauer and Kooiman (1978)

Clytostoma callistegioides (Cham.) Baill. Neg. This work

Cuspidaria pterocarpa (Cham.) DC. Neg. This work
Dolichandra cynanchoides Cham.) 5,7-bisdeoxy Cynanchoside D Adriani et al., 1982
Cynanchoside D Bonini et al. (1981)
Macfadyenoside D Bianco et al. (1974)

Macfadyena unguis-cati (L.) Gentry Neg. This work

Pyrostegia venusta (Ker-Gawl.) Miers Neg. This work

Pithecoctenium crucigerum (L.) Gentry Ipolamiide (6) C This work

Strictoloside (7) C
Theviridoside (5) C
Pseudocalymma elegans (Vell.) Kuhlm. Lamiide (9) C Krebs (1987)
Pseudocalymmoside C Krebs (1991)
Durantoside II C
Tynnanthus elegans Miers Neg. This work
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

Urbanolophium dusenianum (Kraenzlin) Melchior Neg. This work

Crescentieae
Crescentia sp. Aucubin (2) D Hegnauer and Kooiman (1978)
Catalpol (1) D
C. cujete L. Ajugol D Kaneko et al. (1997)

6-O-p-hydroxybenzoylajugol D
Aucubin (2) D
6-O-p-hydroxybenzoyl-6-epi-aucubin (4) D
Agnuside D
5,7-bisdeoxycynanchoside D
Crescentoside A D
Crescentoside B D
Crescentoside C D
Parmentiera sp. Aucubin (2) D Hegnauer and Kooiman (1978)
Coleeae
Kigelia sp. Catalpol (1) D Hegnauer and Kooiman (1978)

`Catalpolestera D Hegnauer and Kooiman (1978)

K. pinnata (Jacq.) DC. Minecoside D Houghton and Akunyili (1993)

Specioside D
Verminoside D
Eccremocarpeae
Eccremocarpus scaber Ruiz and Pav. Mussaenoside (11) C Garbarino and Nicoletti (1989)
Ecremocarpol A (12) D
Ecremocarpol B (13) D
Catalpol (1) D This work
Gardoside methylester (10) C
Oroxyleae

Oroxylum sp. Neg. Hegnauer and Kooiman, (1978)

!C: C-4 carboxyl iridoids; F: C-4 formyl iridoids; D: decarboxylated iridoids; CD: dimeric iridoids consisting of both types
"synonym: Chilopsis saligna D. Don.
G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

#the erroneous genus name Pondranea was used by Guiso (1982).

$synonym: Tecoma chrysantha Jacq.
%synonyms: Tecoma heptaphylla (Velloso) Mart. by Bianco et al. (1983b,c); Tabebuia avellanedae (Lorentz) Griseb. by Nakano et al. (1993).
&synonym: Tabebuia pentaphylla (L.) Hemlet
'synonym: Tecoma speciosa DC.
361

)synonym: Macfadyena cynanchoides (Cham.) Morong.

362 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366

is formed from catalposide (15) by degradation during storage followed by work-up

with ethanol (Hussain and Leonard, 1987).
In Bignoniaceae the presence of C-4 carboxylated iridoid glucosides is not common.
The presence of this kind of iridoids in Argylia radiata (tribe Tecomeae) and in
Eccremocarpus scaber (tribe Eccremocarpeae), two species which both also contain
decarboxylated iridoids, is probably not signi"cant, since the 4-carboxylated com-
pounds found may be considered to be biosynthetic intermediates (or derivatives of
these) on the pathway to the decarboxylated iridoids (c.f. Jensen, 1991). The remaining
three occurrences are all from tribe Bignonieae, where they are found in the species
Pseudocalymma elegans, Adenocalymna marginatum and Pithecoctenium crucigerum.
The tribe Tecomeae is characterized by decarboxylated iridoid glucosides (1, 2 and
their derivatives) and C-4 formyl iridoids (like 3). The compounds with a carboxylic
function at C-4 isolated from Argylia radiata, namely geniposidic acid, mussaenosidic
acid, 7-deoxy-8-epiloganic acid and 7-deoxygardoside (8), are probably not taxo-
nomically signi"cant as discussed above. The mixture of chemical constituents found
in this species is indeed remarkable, but on the other hand, the species is also unique
among neotropical Bignoniaceae because of its herbaceous habit and its (unusual)
alternate leaves (Gentry, 1992).
Morphologically, vines are considered more advanced than trees, and chemically,
decarboxylation or absence of iridoids are considered as a derived state while the
presence of C-4 carboxylated or formylated iridoids usually is considered the primi-
tive state. In Bignonieae, all the species are vines and the greatest part seems not to
present iridoids. However, in the few species where iridoids are present, they are
usually C-4 carboxylated. Decarboxylated compounds are present only in
Dolichandra cynanchoides, previously classi"ed as Macfadyena cynanchoides. Interest-
ingly, besides the occurrence of typical tecomoid iridoids, this monotypic genus of
Bignonieae has normally its fruit split only perpendicular to the septum. Nevertheless,
occasional individuals have incompletely 4-valved fruits and, according to Gentry
(1980), the Tecomoid dehiscence in Dolichandra seems clearly a secondary modi"ca-
tion and Dolichandra should therefore be classi"ed in Bignonieae. Besides that, all
genera of Bignonieae have anomalous wood structure although this is lost in some
individual species of several genera which are su!ruticose or treelets. No genus of
Tecomeae has anomalous wood anatomy, not even the lianas. Thus, the presence of
anomalous wood structure in Dolichandra supports its inclusion in Bignonieae despite
perpendicular-to-the-septum dehiscence. Conversely, the presence of decarboxylated
iridoids would rather indicate an inclusion within Tecomae.
A phylogenetic study of the Bignoniaceae and related families using the DNA
sequences of the chloroplast genes rbcL and ndhF was recently performed by Spangler
and Olmstead (1999). Trees were constructed using both genes in addidition to
a combined data set of the two genes. The analysis led the authors to conclude that the
family may be more derived within the order Lamiales sensu lato than once believed.
The study showed also that the family is monophyletic, excluding Paulownia and
Schlegelia, both previously placed in Bignoniaceae or Scrophulariaceae. According to
our data, Paulownia produces decarboxylated iridoids such as catalpol, aucubin and
macfadyenoside often found in Bignoniaceae but also commonly present in other
 G.L. von Poser et al. / Biochemical Systematics and Ecology 28 (2000) 351}366 363

families of the Lamiales sensu lato. Thus, based alone on the iridoid chemistry, we
cannot suggest the placement of the genus in one or another family. When comparing
the cladogram obtained with the iridoid data, some good correlations were found.
Thus, Tecomeae is split up, with one group of species (Tecoma and Campsis) which
produce formyl iridoids separated from the bulk of the tribe (Tabebuia, Cybistax,
Radermachera and Catalpa) which present decarboxylated iridoids. Jacaranda, a genus
without iridoids, and Podranea, with a formyl iridoid, were found in another branch,
and thus separated from the other genera. Species of the tribes Crescentieae and
Coleeae, producing only decarboxylated iridoids, formed monophyletic groups based
on the phylogenetic analysis. The tribe Bignonieae appears in the tree as a mono-
phyletic group but only four species were included in the cladistic analysis.
Dolichandra, which, as discussed above, produces decarboxylated iridoids, was unfor-
tunately not included in this study.

4. Conclusions

Within the family Bignoniaceae iridoids seem to be most common in the tribe
Tecomeae, where they are decarboxylated or C-4 formylated. In the tribe Bignonieae
iridoids are much less common and if present, they are C-4 carboxylated. The
exception is Dolichandra, which is otherwise dubiously placed in this tribe. In the
tribes Eccremocarpeae and Crescentieae until now only decarboxylated iridoids have
been encountered.
Co-occurrence of C-4 formyl and decarboxylated iridoids within one species (or
even genus) is very rare. This is only seen in Argylia until now. This fact seems to be
useful to distinguish the genera Tabebuia and Tecoma, of which the "rst has decar-
boxylated iridoids, while the latter C-4 formyl compounds.

Acknowledgements

G.v.P. is grateful to FAPERGS and CNPq (Brazil) for "nancial support.

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