An orsellinic acid glucoside from Syzygium aromatica

Article abstract of DOI:10.1016/S0031-9422(98)00091-0

The buds of Syzygium aromatica yielded two triterpenoid acids, oleanolic acid and crategolic acid, and a new phenolic glucoside, orsellinic-2-O-β-D- glucopyranoside, from its methanolic extract. The structure was elucidated by spectroscopic methods and acid hydrolysis.

Full text of DOI:10.1016/S0031-9422(98)00091-0

Phytochemistry\ Vol[ 38\ No[ 4\ pp[ 0264Ð0265\ 0887
Þ 0887 Elsevier Science Ltd[ All rights reserved
Printed in Great Britain
Pergamon
\
9920Ð8311:87:,*see front matter
PII ] S9920Ð8311"87#99980Ð9
AN ORSELLINIC ACID GLUCOSIDE FROM SYZYGIUM AROMATICA
REENA CHARLES\ SHRI NIWAS GARGꢀ and SUSHIL KUMAR
Department of Phytochemical Technology\ Central Institute of Medicinal and Aromatic Plants\ LucknowÐ115904\
India
"Received in revised form 1 February 0887#
Key Word Index*Syzy`ium aromatica ^ Myrtaceae ^ orsellinic acid glucoside[
Abstract*The buds of Syzy`ium aromatica yielded two triterpenoid acids\ oleanolic acid and crategolic acid\
and a new phenolic glucoside\ orsellinic!1!O!b!D!glucopyranoside\ from its methanolic extract[ The structure
was elucidated by spectroscopic methods and acid hydrolysis[ Þ 0887 Elsevier Science Ltd[ All rights reserved
INTRODUCTION
acid ð8Ł\ and a phenolic glucoside "0# orsellinic!1!O!b!
D!glucopyranoside[ Chemical analysis and the mass
spectrum of compound 0 showed it to have the molec!
ular formula C03H07O8[ IR absorption bands at 2389
and 0557 cm−0 were indicative of hydroxy and car!
boxyl groups\ respectively[ The presence of a carbonyl
group was further con_rmed by the presence of a
Syzy`ium aromatica "L[# Merr and Perry\ a tree
commonly known as clove\ is indigenous to the
Moluccas[ In India it is cultivated in Kerala\ Tamil
Nadu\ Karnataka\ and Andaman and Nicobar
Islands[ Clove buds "whole or ground# are mainly used
as a spice for domestic culinary purposes and for the
industrial manufacture of sauces and pickles ð0Ł[ The
essential oil obtained from distillation of the buds is
of the highest quality and _nds extensive use in the
perfumery and ~avouring industries and to a limited
extent in the pharmaceutical industry[ This oil shows
antibacterial activity ð1Ł\ while the acetone extract of
buds shows anticholagouge activity ð2Ł[ Eugeniin\ a
compound isolated from the ethyl acetate extract of
clove buds shows antiviral activity ð3Ł[ Most studies
ð4Ð6Ł have been concerned with the chemical con!
stituents of the essential oil[
Despite its great importance in Indian perfumery\
~avouring and pharmaceutical industries\ S[ aro!
matica had been the subject of limited investigation[
This study has revealed the presence in the buds of
oleanolic acid "which is already used as a drug in
China ð7Ł for the treatment of jaundice#\ crategolic
acid and a new phenolic glucoside\ orsellinic!1!O!b!
D!glucopyranoside[
0
signal at d 073[23 in its 02C NMR spectrum[ The H
NMR spectrum revealed the presence of two meta
coupled aromatic protons at d 4[82 "d\ J ꢁ 1 Hz# and
5[98 "d\ J ꢁ 1 Hz# and a singlet at d 1[14 "2H# indica!
tive of an aromatic methyl group[ Signals at d 051[79\
055[74 and 032[80 were attributed to C!1 and C!3 of
the benzene ring\ and a ring methyl group at C!5\
0
respectively ð09Ð03Ł[ Further signals in the H NMR
and 02C NMR spectra clearly indicated the presence
of a glucose moiety[ A one proton doublet at d 3[67
"J ꢁ 6 Hz# was assigned to the b!anomeric proton
which was further supported by the chemical shift in
the 02C NMR spectrum at d 093[69[ Hydrolysis of
compound 0 with methanolic HCl a}orded two prod!
ucts ^ a sugar which was identi_ed as glucose by paper
chromatography and an aglycone identical to orsel!
linic acid "mp[\ mmp and Co!TLC#[ Thus\ from the
above spectroscopic and chemical data\ compound 0
was concluded to be orsellinic!1!O!b!D!glucopyra!
noside[
RESULTS AND DISCUSSION
EXPERIMENTAL
The methanolic extract of S[ aromatica buds yielded
Mp ] uncorr[ ^ NMR ] 199 MHz "0H# and 49 MHz
"02C# CD2OD with TMS as int standard ^ MS ] 69 eV
"direct inlet# ^ TLC ] Merck silica gel 59 F143 plates\
spots visualised by spraying with a 0) sol of vanillin
in H1SO3 followed by heating at 009> for 04 min ^ CC ]
silica gel "59Ð019 mesh#[
two triterpenoid acids\ oleanolic acid and crategolic
ꢀAuthor to whom correspondence should be addressed[
Tel ] 99 80 231565 ^ Fax ] 99 80 411231555 ^ E!mail ] root!
Ýcimap[sirnetd[ernet[in[ CIMAP Communication No[ 86Ð
88 J
0264

0265
R[ CHARLES et al[
ðM−H1OŁ¦ "7#\ 057 "89# "Found ] C\ 40[0 ^ H\ 49[27[
C03H07O8 requires C\ 49[38 ] H\ 4[34)#[
Acid hydrolysis of 0[ Compound 0 "17 mg# in MeOH
"1 ml# was re~uxed with 4) HCl "1 ml# for 3 h in a
water bath[ After cooling\ the reaction mixture was
extracted with EtOAc[ The EtOAc layer was dried
over MgSO3 and concd under reduced pressure[ The
extract was recrystallised from MeOH to give 1 "09
mg#\ mp 058Ð069>\ which was identi_ed as orsellinic
acid by TLC\ mp\ and mmp[ The aq[ layer was pro!
cessed for sugar[ This sugar was identi_ed as glucose
by comparison with a standard sample on PC "BuOHÐ
HOAcÐH1O\ 3 ] 0 ] 4#\ using aniline hydrogen phthal!
ate as the spray reagent[
Acknowled`ements*We are grateful to the Head of
the Phytochemical Technology Division for providing
facilities and encouragement throughout the work[
R[S[I[C[ Lucknow is thanked for recording the 199
0
MHz H NMR and 49 MHz 02C NMR and mass
spectra[ Dr G[ N[ Srivastava is gratefully thanked for
help in procuring the genuine plant material[
REFERENCES
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Plant material
S[ aromatica was purchased from the local market
and a specimen voucher has been deposited at the
Institute herbarium[
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Extraction and isolation
Powdered buds of S[ aromatica "0[4 kg# were
extracted with n!hexane\ CHCl2 and MeOH[ The sol!
vents were removed in vacuo to give three frs weighing
001[4 g\ 099[4 g and 084 g\ respectively[ Fifty grams
of the MeOH extract on CC on silica gel using hexane\
hexaneÐEtOAc\ EtOAc and EtOAcÐMeOH\ a}orded
oleanolic acid "0 g#\ crategolic acid "29 mg# and com!
pound "0# "39 mg#\ Rf 9[43 in CHCl2ÐMeOH "2 ] 0#[
Orsellinic!1!O!b!D!glucopyranoside "0#[ Colourless
crystals "MeOH#\ mp 089Ð080>\ ðaŁ0D7 ¦1[3> "c 0[9 ]
MeOH
max
KBr
max
MeOH#[ UV ðlŁ
nm ] 144 and 184 ^ IR ðnŁ cm−0
]
2389\ 2168\ 1810\ 1801\ 0557\ 0504\ 0431\ 0346\ 0310\
0275\ 0219\ 0157\ 0119\ 0917\ 756\ 739 and 624 ^ H
0
NMR "199 MHz\ CD2OD# ] d 1[14 "s\ 2H\ CH2#\ 2[29
to 2[27 "m\ 1H#\ 2[47 "dd\ J ꢁ 01\1 Hz\ 0H#\ 2[61 "dd\
J ꢁ 01\4 Hz\ 0H#\ 2[86 "dd\ J ꢁ 01\1 Hz\ 0H#\ 3[67 "d\
J ꢁ 6 Hz\ 0H#\ 4[82 "d\ J ꢁ 1 Hz\ 0H#\ 5[98 "d\ J ꢁ 1
Hz\ 0H# ] 02C NMR "CD2OD# ] d 19[87 "CH2#\ 51[80
"C!5?#\ 61[75 "C!3?#\ 64[38 "C!1?#\ 67[89 "C!4?#\ 79[91
"C!2?#\ 099[61 "C!2#\ 093[69 "C!0?#\ 094[21 "C!0#\
097[64 "C!4#\ 032[86 "C!5#\ 051[79 "C!3#\ 055[74 "C!1#\
073[23 "C!7# ^ EI!MS m:z "rel[ int[# ] 229 ðMŁ¦ "4#\ 201
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