Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Phytahmusrry.
Vol
1994
Lld
TRITERPENOIDS
$6.00+0.00
SHOREA ROBUSTA*
robusta; Dipterocarpaceae;
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
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
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].
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