Pergamon 0031-9422(94)00739-X Phytochemistry, Vol. 38, No. 3, pp.

687 689, 1995

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TRITERPENOIDS A N D CHALCONE FROM S YZYGIUM SAMARANGENSE*

RACHANA SRIVASTAVA,ARUN K. SHAW and DINESH K. KULSHRESHTHA~"

Medicinal Chemistry Division, Central Drug Research Institute, Lucknow 226001, India

(Received in revisedform 23 August 1994)

Key Word Index--Syzygium samarangense; Eugenia javanica; Myrtaceae; triterpene methyl ester;
chalcone; ursolic acid; jacoumaric acid; arjunolic acid.

Abstract--A new triterpene, methyl 3-epi-betulinate in its native form and 4',6'-dihydroxy-2'-methoxy-3',5'-dimethyl
chalcone along with ursolic acid, jacoumaric acid and arjunolic acid have been isolated from the aerial parts of
Syzygium samaran.qense.

INTRODUCTION LAH reduction. Isolation of 3-epi-betulinic acid has been

reported earlier and its methyl ester was also prepared [3]
Syzy#ium samarangense (syn. Eugenia javanica Linn.)
but to the best of our knowledge epi-betulinic acid methyl
occurs in Andaman and Nicobar Islands, India. It is
ester as such has not been reported previously from a
cultivated in many parts of India for its edible fruit [1].
natural source.
The alcoholic extractive of the plant Syzygium samaran-
Another compound (2) isolated from the plant gave a
gense exhibited immunostimulant activity in the general
characteristic olive-green colour reaction for chalcones
biological screening programme of CDRI. So far no
with freshly prepared FeCI 3 [4]. The IR spectrum of the
significant work on this species is reported in the literat-
chalcone displayed absorption bands for a free hydroxyl
ure. Therefore, a detailed chemical investigation on this
as well as a H-bonded hydroxy group (3360 and
plant was undertaken.
2960 cm- t) and for ~t,fl-unsaturated C=O (1620 c m - 1).
Its I H N M R spectrum exhibited signals for a mono-
RESULTS AND DISCUSSION substituted phenyl group at 67.42 and 7.65, a trans-
The chloroform fraction of the alcoholic extract of the disubstituted double bond at 67.87 and 8.00 (JAB
aerial part of the plant on column chromatography over = 16.0 Hz), two benzylic methyl groups at 62.17 and 2.20
silica gel yielded five compounds. and one aromatic rnethoxyl at 63.70. Furthermore, two
Compound 1, C 3 t H 5 0 0 3 , ([M] + at m/z 470), was signals at 613.62 and 5.37, respectively, which disap-
found to be a new triterpene ester (responded positive to peared on D 2 0 shake were ascribed to two hydroxyl
the Liebermann-Burchardt test) identified as methyl 3- groups, one of which was strongly hydrogen bonded. The
epi-betulinate (mp 220 °, [ct] 25 - 10, CHCla; c0.192) on El-mass spectrum of 2 showed [M] + at m/z 298 and a
the basis of its mass fragmentation and NMR spectra. base peak ofm/z 91. One of the fragments at m/z 166 was
Compound 1, on acetylation, gave a monoacetate la, indicative of a highly substituted phenyl ring with two
C 3 3 H 5 2 0 4 ( [ M ] + at m/z 512, 62.07, 3H, s, OCOMe). The
hydroxyl, two methyl and one methoxyl groups. Thus,
low W1/2 value (6.75 Hz) of the C-3 methine proton in the from the above spectral data, it became clear that the
1HNMR spectra of 1 (63.38, 1H, br s, CHOH) and l a chalcone had a 2',4',6'-trioxygenation pattern which
(64.60, 1H, br s, CHOAc) suggested that it had the fl- could lead to either of the two possible structures 2',6'-
configuration and the C-3 oxygen function, therefore, had dihydroxy-4'-methoxy-3',5'-dimethyl chalcone (2a) or
the ~-configuration. It was also observed in the t3C 4'-6'-dihydroxy-2'-methoxy-3',5',-dimethylchalcone (2b).
spectrum of 1 that C-3 appeared upfield by about 3 ppm However, the chalcone was assigned the structure 2b on
as compared to the corresponding carbon in methyl the basis of its NOE difference spectrum which showed
betulinate [2]. Finally, the confirmation of the compound that the irradiation of the signal at 63.70 (OMe) resulted
I as methyl 3-epi-betulinate was achieved by converting it in the enhancement of only one of the C-methyl signals at
to betulin (lc, H-3 at 63.21, dd, J = 11.0 and 5.5 Hz) [2] 62.20 and also one of the olefinic signals at 68.00
by first oxidizing 1 to the keto derivative lb followed by (PhCH_ =CHCO). These observations suggested that the
methoxyl group was in close proximity to only one of the
C-methyls (3') as well as a fl-olefinic proton. The
13C NMR spectrum of 2 (Table 1) showed the presence of
*CDRI communication No. 5282. carbon carrying one methoxyl and two hydroxyl groups
tAuthor to whom correspondence should be addressed. with signals at 6162.1,159.3 and 130.2, respectively [5, 6],

687
PHYTO38-3-J
688 R. SRIVASTAVAet al.

Me

R10 ~ O R 2 [ H ~

RI .=
0 0
H"

R1 R2 R3 R1 R2

1 H OH COOMe 2,a Me H
la H OAc COOMe 2.b H Me
lb O O COOMe
lc OH H CH:zOH

Table 1. t3CNMR spectral EXPERIMENTAL

data for compound 2b
Plant material. Syzygium samarangense (aerial part)
(100 MHz, CDC13)
was collected from Chiriatapu (South Andaman, India).
C 2b A voucher specimen of the plant is deposited in the
herbarium of Botany Division, CDRI.
1 135.4 General. Mps: uncor.; IR: KBr; UV: MeOH, EtOAc;
2 128.9 I H N M R : 400 MHz, TMS as int. standard; 13CNMR:
3 128.4 100 MHz; EI-MS: direct inlet 70 eV; CC silica gel; TLC:
4 130.2 silica gel coated plates using solvent systems (1) C6H 6 (2)
5 128.4 CHC13-MeOH (24: 1), (23:2), (3) C6H6-MeOH (23:2).
6 128.9 TLC chromatograms were visualized by spraying with
fl 142.9 1% ceric sulphate in 1 M H2SO 4 followed by heating at
ct 126.8
l l 0 °.
C=O 193.4
1' 106.6 Extraction. The alcoholic extractive (38 g) of the plant
2' 162.1 (aerial part 880 g) was resolved into n-C6Hlg, CHC13, n-
3' 108.9 BuOH and H 2 0 soluble fractions. The CHCI 3 soluble
4' 159.3 fraction (13 g) was chromatographed over silica gel. The
5' 109.1 column was eluted with n-C6Hv, and n-C6H1,-EtOAc
6' 130.2 (19: 1) in succession.
OMe 62.3 Isolation of methyl 3-epi-betulinate (1). The eluate n-
Me 8.2 C6H14-EtOAc (19: 1) yielded compound 1 (20 mg) which
Me 7.5 was crystallized from n-C6Ht,-Me2CO; mp 220 °, [~]25
-- 10° (CHCI3: c0.192), ll/ KBrc m - 1: 3550, 1720. ELMS
--- Vm,x
m/z: 470 I-M] +, 452 l,M - 181 +1, 411 [M - CO2Me] +,
262, 233, 220, 207, 203, 189. I H N M R : 60.83, 0.85, 0.92,
0.93, 0.97, 1.68 (3H each, s, 6 x C-Me), 3.00 (1H, dr, J
along with a low field signal at 6193.4 due to a chelated = 10.5, 4.2 Hz, H-19), 3.38 (1H, br s, W l / 2 = 6.8 Hz,
carbonyl carbon. Although the isolation of both the C HOH), 3.68 (3H, s, OMe), 4.61 and 4.75 (1H each, d, J
chalcones, 2a and b, has already been reported [7, 8] from = 2.0 Hz, C=CH2-29 ).
Myrica #ale, the isolation of 2b from Syzyfium samaran- Isolation of chalcone 2. Another n-C6H14-EtOAc
gense constitutes the second report from a natural source. (19:1) eluate of the gross chromatography furnished
The assignment of its 13C NMR spectrum is reported for chalcone 2 (40mg) which was crystallized from n-
the first time. C6Htg-Me2CO; mp 120°; IR vm, x cm- t: 3360, 2960, 2340,
KBr
Other triterpenoids isolated from this plant were iden- 1620, 1540, 1440, 1350, 1220, 1160, 1100, 970, 900, 810,
tified as ursolic acid, jacoumaric acid and arjunolic acid 750, 680. UV 2m.x
racon nm: 332.8 and 204.8; •EIOAe
max n .Ill:
. . .'-I'U"t.O,
.
(as the major constituent of the plant) by their spectral 303.2 and 212.0. EI-MS re~z: 298 [M] +, 221 [M - 77] +,
data (IR, EI-MS, tH and 13CNMR) as well as by 206 [M - 92] ÷, 194 l,M - (Ph~CH=CH) - H] +, 166
preparation of their acetates and methyl ester derivatives [194 - CO] +, 165 1-194 - HCO] +, 131
and comparing their spectral data with those reported in I,PhCH=CHCO] +, 103 [PhCH=CH] +, 91 [Ph - CH 2
the literature [9-11]. - base peak] +, 77 [phenyl ring]: 1H NMR: 32.17 (3H, s,
 Triterpenoids and chalcone from Syzygium samarangense 689

C-Me), 2.20 (3H, s, C-Me), 3.70 (1H, s, OMe), 7.42 (3H, m), 4. Khalilullah, M. D., Sharma, V. M. and Rao, P. S.
7.65 (2H, m), 7.87 and 8.00 (1H each, d, AB-system, JAB (1993) Fitoterapia 3, 232.
= 16.0 HZ), 5.37 and 13.62, (1H each, s, disappeared on 5. Markham, K. R., Chari, V. M. and Mabry, T. J. (1982)
D20 shake). 13CNMR: see Table 1. in The Flavonoids: Advances in Research (Harborne,
J. B. and Mabry, T. J., eds), p. 19. Chapman & Hall,
Acknowledgements---The authors are grateful to Dr B. N. London.
Mehrotra for collection and identification of the plant 6. Roitman, J. N., Wong, R. Y. and Wollenweber, E.
materials and to the staff of the Regional Sophisticated (1993) Phytochemistry 34, 297.
Instrumentation Centre, CDRI, Lucknow, for spectral 7. Anthonsen, T., Falkenberg, I., Laake, M., Midelfart,
data. A. and Mortensen, T. (1971) Acta Chem. Scand. 25,
1929.
8. Malterud, K. E., Anthonsen, T. and Lorentzen, G. B.
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