Pergamon

Phytahmusrry.

Vol

35. No. 4, pp. 1073-1074.

Sacna
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1994
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TRITERPENOIDS

FROM THE RESIN OF

$6.00+0.00

SHOREA ROBUSTA*

Rlu K.HOTA and MARINGANI-IBAPU~~

Regional Research Laboratory, Bhubaneswar-751013, Orissa, India
(Received in revised form 23 June 1993)

Key Word Index-Shorea

nor-urs-12ene.

robusta; Dipterocarpaceae;

resin; ursane triterpenoids; new 3/?-acetoxy-2%

Abstract-From
the resin of Shorea robusta, in addition to three known triterpenoids, a new nor-triterpene 3/?acetoxy-28-nor-urs-12-ene
has been isolated. The structure of the new triterpene was established by photochemical
conversion and spectroscopic studies.

INTRODUCTION

Raal, the resin of Shoreu robusta Gaertn (Dipterocarpaceae) is abundantly available in India and has been widely
used in the indigenous system of medicine as an astringent and an ingredient in ointments for skin diseases, and
in ear troubles [l]. Earlier work on this resin reported the
isolation of several known triterpenoids [2]. In our
previous communication, from sal resin we have reported
the occurrence of six more triterpene acids; ursolic acid;
2a,3Bdihydroxy-urs-12-en-28-oic
acid; 2z,3a-dihydroxyurs-12en-28-oic
acid; 3/?,23-dihydroxy-olean-12cn-28oic acid; 2a,3/?, 23-trihydroxy-urs-12en-28-oic
acid; and
2&3B,23-trihydroxy-1 l/?-methoxy-urs-12-en-28-oic
acid
[3]. We now report the isolation of four more triterpenes;
28-nor-urs- 12-en-3B-ol, 1; ursaldehyde, 4; ursaldehyde
acetate, 2; a 3/?-acetoxy-28-nor-urs-12ene,
3, and acetate of 1, hitherto not reported from nature. Of the three
known triterpenes, 1 was earlier isolated from the fruit of
Symphoricarpus albus and was identified by GC-MS [4].

R'
1
2
3
4

BOH
BOAC
BOAC
BOH

R2
H

R3
H

CHO

H
H

H
CHO

RESULTS AND DWXJS!SION

The chromatographically
pure 3 was obtained as
an amorphous
powder, which responded to the
Liebertnann-Burchard
test. (EI) mass spectrum (M+454)
and elemental analysis support the molecular formula
C3,H5002 for the compound. The IR spectrum of 3
showed carbonyl absorption at 1720 cm- 1 and acetate
(C-G) at 1240 cm- . The major fragment ion peaks at
m/z 250 and m/z 204 in the mass spectrum indicated a
typical retro Diels-Alder cleavage of either a- or Bamyrin skeleton, lacking one angular methyl group of
ring D or E [S]. The olefinic carbon signals (123.5, C-12,
138.0, C-13) supported the ursane skeleton [6]. The
*H NMR spectrum of 3 revealed signals for five tertiary
methyls at 60.85,0.91,0.97, 1.10, 1.25 and two secondary
*Part 2, for Part 1 see ref. [3].
TAuthor to whom correspondence should be addressed.

mlz 204

AC0

methyls as doublets at 60.89 (5=6 Hz) and 0.91 (J

= 6 Hz). The peak observed downfield at 6 1.25 could be
readily ascribed to the 27-methyl group [7J The
HNMR spectrum of 3 was very similar to that of 2
1073

Short

1074

(ursaldehyde
acetate) except for the absence of the
aldehyde signal and the presence of a multiplet at 6 1.90
due to the C-18 proton [8]. The signals at 62.08 (3H, s)
and 5.18 (1 H, t, J = 3.4 Hz) showed the presence of an
acetoxy proton and a vinylic proton, respectively. A one
proton dd observed at 64.64 (J = 6 and 10 Hz) could be
assigned to the C-3 a-proton. The C NMR signals of 3
were in good agreement with those of 2 (ursaldehyde
acetate), except that the signal due to the C-28 aldehydic
carbon is missing in the former. Further, while comparing
the 13C NMR spectrum of 3 with that of r-amyrin [9] it
clearly showed that the molecule lacked C-28, because the
methyl resonance at 627.3 was missing.
Interestingly,
2, when kept for six-seven
days in
diffused sunlight yielded 3 in appreciable
quantities
(z 15%). When exposed to direct sunlight for 3-4 hr, 2 is
partially converted to 3 as confirmed by comparison
of
spectroscopic
data. The spectroscopic
and photochemical data thus indicate that 3 is the decarbonylation
product of 2.
All the data given above support the structure of 3 to be
3p-acetoxy-28-nor-urs-12-ene.
The co-occurrence
of aamyrin. ursaldehyde, urosolic acid and 28-nor-urs- 12-en3/I-01 in sat resin is parallel to what is reported from the
resin of Pistacia lent&us by Marner et al. [IO].
EXPERIMENTAL

Optical rotations were measured in CHCI, at 25 mps

are uncorr. H NMR spectra were recorded in CDCI, at
400 MHz. 13C NMR spectrum was recorded in CDCI, at
100 MHz. Chemical shifts are given on the 6 (ppm) scale
with TMS as int. standard. MS: 70eV, EI, IR: CHCI,;
TLC and CC: silica gel GF,,, (aSC) and silica gel (6C- 120
mesh aSC), respectively. The spots on TLC were visualized by spraying with H,SO, (10% in MeOH) and
heating at 120.
Plant material. The resin of S. robusta was collected
from the Tribal Development
Co-op, Corporation
of
Orissa in January 1990. The trees in the area have been
identified and voucher specimens kept with Dr M. Brahmam, Taxonomist,
Aromatic and Medicinal Plant Division, RRL-Bhubaneswar.
The seedlings raised are maintained in the experimental
gardens of the laboratory.
Extraction. The resin (100 g) was extracted
with
MeOH. The MeOH extract was coned under red. pres. to
give a gummy material (63 g) which was extracted with
petrol and C,H,, successively. The petrol extract (log)
was chromatographed
on a silica gel column with
petrol-&H,
(1: I) and C6H, as eluent, yielding 4 frs a-d.
Fr. a showed A at 3525 cm- , indicating the presence of a
hydroxyl group, and no ester carbonyl was observed. It
resisted purification by normal chromatography,
so it was
acetylated with Ac,O-pyridine
and the acetylated product on prep. TLC afforded a compound (7 mg) whose IR,
mass, H, 13CNMR were identical with 3. Thus, the
compound
was identified as 28-nor-urs-12-en-3/&ol,
1.
Prep. TLC of un-acetylated
frs b-d afforded 2 (15 mg), 3
(5 mg), 4(20 mg). Compounds 2 (ursaldehyde acetate) and
4 (ursaldehyde) were identified by spectroscopic data (IR,

Reports

H NMR, mass, 13C NMR) and comparison

with available literature.
Ursaldehyde acetate (2). Mp 209-210. IR v::~J cm- I:
1730, 1380, 1370, 1240, HNMR
(4OOMHz, CDCI,);
SO.75,0.82,0.84,0.94,
1.13 (each s, 3H), 0.85 (d, 5=6 Hz),
0.95 (d, 5=6Hz),
2.10 (s, 3H, Me-CO,), 1.98 (IH, d, ./
=lOHz,H-18),4.62(1H,dd,5=6and
lOHz,H-3r),5.20
(lH, t, J=3.3 Hz, H-12). 9.30 (lH, s, H-CO). EIMS
(70 eV) m/z (rel. int.), 482 [M] (4). 422 (3). 232 (18). 203
(100).
3/I-acetoxy-28-nor-urs- 12-ene (3). Amorphous powder.
[a]$+31
(CHCI,; c 0.47), (Found: C, 81.49; H, 11.01.
C,,H,,O,
requires: C, 81.53; H, 11.03%). IR vEF3 cm-:
1720, 1240, HNMR
(400 MHq CDCI,); 60.85, 0.91,
0.97, 1.10, 1.25 (each s, 3H), 0.89 (d, 5=6 Hz), 0.91 (d, J
=6 Hz), 2.08 (3H, s, Me-CO,), 5.18 (IH, t, J=3.4Hz),
1.90(1H,m),4.64(1H,dd,J=6and10Hz).EIMS(70eV)
m/z (rel. int.) 454 [M] (lo), 394 (4), 379 (4), 250 (3), 204
(100). 13C NMR (100 MHz, CDCI,); 638.4 (C-l), 23.7 (C2). 78.3 (C-3), 37.8 (C-4), 53.2 (C-5), 18.3 (C-6). 32.4 (C-7),
40.1 (C-8),47.5(C-9),37.1
(C-lo), 17.7(C-ll), 123.5(C-12),
138.O(C-13), 40.9 (C-14), 29.7 (C-15), 27.1 (C-16). 50.2 (C17). 58.0 (C-18), 39.7 (C-19). 39.8 (C-20), 31.3 (C-21), 40.1
(C-22), 27.9 (C-23). 17.1 (C-24), 15.4 (C-25). 16.8 (C-26),
23.1 (C-27), 22.8 (C-29), 22.0 (C-30).
Ursaldehyde (4). Amorphous
powder. IR vZ!.F~
cm- l:
3520, 2900, 1730, H NMR (400 MHz, CDCl,): 60.74,
0.81,0.84,0.93, 1.13 (each s, 3H),0.85 (d,J=6 Hz), 0.95(d,
5=6 Hz), 1.98 (lH, d, .I= IO Hz), 3.4 (lH, dd, H-3a), 5.34
(lH, t, H-12), 9.3 (lH, s, H-CO). EIMS (70eV) m/z (rel.
int.) 440 [M] (8), 232 (l5), 203 (100).
Acknowledgements-We
thank IICT-Hyderbad,
RSIC,
CDRI, Lucknow, CCMB, Hyderabad,
for the spectral
facilities; Director, RRL-Bhubaneswar,
for providing laboratory facilities and support. One of us (R.K.H.) thanks
CSIR for a Senior Research Fellowship.
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