Escolar Documentos
Profissional Documentos
Cultura Documentos
CHEMICAL
RESEARCH
COMMUNICATIONS
VOL.16,2003
∧ :nternationa:
Program in the
UNESCO
Chemical ScienOes
(IPiCS)
Cover page: The cover page includesthe structureof the alkaloid actinodaphninewhich was
subject of the first paper published in ACGC Chemical Research Communications. This
kaloid was isolated from the root bark of Zirsea diversifolia from the district of Subang,West
Java,Indonesia.
Members
Dr. M. Akerblom (IPICS)
Dr. J. R. Cannon (Australia)
Prof. B. H. Han (Korea)
Prof. S. Hill (UNESCO)
Dr. Nordin Bin Haji Lajis ({INESCO-SE Asian
Regional Network)
Dr. Rune Liminga (IFS)
Assoc. Prof. B. Noller (Secretary, Australia)
Dr. Mohinder Singh (IKM)
Prof. J. Webb (Australia)
Hesham R. El-Seedi
KamaruzzamanBin Yunus
Rapid Synthesis of a model chrymutin like compound and its derivatization in weak
alkaline or in neutral medium.
H. N. Roy, A. M. Paul and M. S. Sarkar 74
ACGC ChemicalResearchCommunicationsVol. 16, 2003 - Page19
and Atta-ur-Ratrmant
Received25'hNovember.2002
Abstract
A new triterpenoid, 23-hydroxy-24-methylenecycloartanol, and the known compounds, lupeol,
and
and sitosterol-3-O-B-glucopyranoside
oleanolic acid, stigmasterol-3-O-B-glucopyranoside
betulin, were isolated from the aerialparts of Sarcococcacoriacea (Hook. F.) Sweet(Buxaceae).
Their structures were assigned on the basis of spectral data. The dichloromethane extract was
found cytotoxic while the methanol extract showed enzpe inhibition of polygalacturonase.
Keylvords: Sarcococcacoriacea(Hook. F.) Sweet;Aerial parts; Triterpenoid
Introduction
Sarcococca coriacea (Hook. F.) Sweet, Buxaceaeris an evergreen shrub widely distributed in the
Mahabharat range of Himalayan Kingdom of Nepal. The plant has exhibited antibacterial,
anticholinesterase,antitumor, antiulcer and ganglion blocking' properties. Different parts of the
plant are harnessedin the treatment of fever and rheumatism in traditional medicine.' A number
*
To whom correspondenceshould be addressedTel: 977-01-332034, 977-01-260384Email:
nara@nar_ni.wlink.com.np
i Central Department of Chemistry, Tribhuvan University, Kathmandu, Nepal,
t H.E.J ResearchLrstitute of Chemistry, lnternational Center for Chemical Sciences,University
of Karachi, Karachi-7 5270, Pakistan
$ Sho*a PharmaceuticalUniversity, Machida, Tokyo 194-8543, Japan
ИC G C C t t θ t t C″″露
α′R ♂θαr ε
″J σ ο ηJ σ
αι 4 s レb l ′こ 2 θθg _ P a g e 2 0
Jο
the isolation of a new triterpene l along with known compounds, lupeo1 2, oleanolic acid 3,
‐
stittasterol-3-0-β ‐
glucOpyranoside 4,β ―
sitOSterol-3-0-β
glucOpyronosice 5 and betulin4 6
smctures Ofthe isolated compounds are assigned rnainly on the basis oftheir spectral data.
residue.The residue was partitioned between distilled water and hexane,then dichloromethane.
The dichloromethane extract was suttected tO Colllmn chromatography to afford compounds l-6.
198-200°
C,blg+85.7° ons江 3400(OH),
(60.9,veoH)・ The R spectmm displayed absorp■
1.EIMS ga■ /e a molecular ion pcak at“ /_-456
2900(CH),1600(olCin),1020(C― O)Cm‐
(C31H5202)and the peak at“ /z441 ducto M+― CH3・ The base peak at″ ル 438 was due to the loss
- 4 2 3 , 4 2 0 , 4 0 5 a n d 3 9 5 w e r e a s s i g n e d H 2f 0o r C[ HM 3―1 ' , [ M
o f w a t e r i o m M + . T h e p e a k s a/t_〃
signals(H2 28)at 4.918 and 5.018 were also assigned.A pair of doublets at O.329 and O.547,with
and 4.210(J=6.4,6.4 Hz)were assigned for the protons at H-3 and H-23 respectively.
NMR spectrum showed the presence of thirty― one carbons in the molecule. The DEPT 135
spec― showed twenty flve carbon signals with fourteen positive and eleven negative signals.
Analysis of the l)EPT-90 specmm revealed seven CH and seven CI13 CarbOns in the l■ olcculc,
w h i c h w a s i r t h c r s u p p o r t e d Nb My R .l SH i‐x p e a k s f o r c a r b o n m i s s i)nmg 魚
the DEPT-135 were
assigned as quatemary.
The partial structures for五ngs A,B and C were S01Ved by detailed analysis of I‐ IMBC
C-22-C-23 were detel.1.ined ttЮm analysis of HMBC and COSY spectra.Thc chernical shi■ s of
carbons in五 ngs A,B,C and lD are vcry close to CyC10artanc denvatives.Also,analysis of the
mass specm of cOmpound l indicated that it Was a de五 Vative of the 4,4‐diinethyl tン
pe of
chain carbon,as depictOd in Fig.4. On the basis of
cycloartane triterpenOid Ⅵ/ith an extra side―
ИC C C C 力θ“J c α αr c 力σο″“z ηi C α
′R “ θ ″0 “s レb i f a 2 θ
θ3 - P a g e 2 1
spectroscopy,dircct companson with an authentic sample(mmp and co― tlc)and the reported
NNIIR spectroscopy, companson with spcctral data6, and direct companson with an authentic
spectral data7,8 and an authentic sample(mmp and CO― tlc),the cOmpound was assigned as
stigmasterol-3-0-β―D‐glucopyranoside.
C.The
Compound 5(C35H6006)WaS iSOlated as a white crystalline solid,m.p.253°
―
co m p o l l n d was assigned as sitostcrol-3-0-β
glucOpyranoside by dircct compa r i s o n w i t h
tlc).
authentic salnplc(mp andCO―
Compound 6 is idcntifled as betulin by companson、 m value of
/ith the reported lH―
betulin 8.
Experilnental
Gι″eraJ IhηθrliHθ
″″′Practtts=l■lelting points werc uncorrected,and were recorded on an
electnc Sun―Vic U.K.IR‐ spectra were recordcd in KBr discs.lH― NMR(400 Ⅳ EIz)speCtra Of
and DEPT spectra of compollnds l and 2 were recorded on a Bruker AC-300 operating at 75
NEHz.lH― NNIR(500 MHz)ofcompounds 4,5 and 6 were rccordcd on JEOLα -500 speOtrometer.
The chemical shift(δ)values are cxpressed in ppm units,and coupling constants(の are」 ven in
Hz.The mass spectra were recorded on a JEOL― 」NIS―D300 14ass spectrolneter.Pre―coated TLC
plates(G254)Were uSCd to check the polanty ofthe compounds,and silica gel(60-200 mesh,E
MerCD Was used for collllllm chromatography.
r s M a ″r l i a JTsh「e p l a n t m a t ea 五
PJa“ ls were collected iom Hattiban,Kathnandu in September
to afford compolmds(1‐ 5).Eluting the colum with pllre cthyl acetate gave a fcW iactions
contalmng two components. The Ⅱ lixture was dissolved in ethyl acetate and a few drops of
hexane added until turbid. On standing, a crystallinc compound separated.The compound was
C ; [ α] 『 + 8 5 . 7 °
恥h i t e c r y s t d u n e s o mh .とp . 1 9 9 ° C(cO.9,MCO菫 ゝR vtt cm・ :33oO,2900,
(2H,H-11),1.63,1.63(2H,H-12),1.28,1.28(2H,H-15),1.10,1.98(2H,H-16),1.66(H-17),
20):4.210(dd,lH,」
1.38∈ I‐ =6。2,6.4 Hz,H-23),2.319(lH,dq,J=6.4 Hz,H-25);13c_NMR
+456(29),438(100),423(69),420(16),405(20),395(35),
(CDC13),SCe Table l;EIMS″ /z[ゝ凋
309(32),316(96),297(55),255(28),123(93).
H-24),0.828(3H,s,H-25),1.029(3H,s,H-26),0.943(3H,s,H-27),0.787(3H,s,H-28),4.562
(td,lH,J=1.0,1.0,1.OI‐Iz,H-29),4.682(d,lH,J=2.2 Hz,H-29)1.678(3H,s,H-30),3.184,(d,
lH,J=10.5 Hz,H-3),1.653,0.906(2H,H-1),1.529,1.598(2H,H-2),0.680(d,lH,」 =9.0耳 z,H―
5),1.405,1.521(2H,H-6),1.388,1.385(2H,H-7),1.286(H‐ 9),1.235,1421(2H,H-11),1.078,
189(72)
θ物 ″οJ l i c″ J Ⅱn e s o Ⅱ
∠ の 「W h i C C r y 償 C , L ] 『 + 9 7 . 0 ( σ α1 4 M c O H ) V t t C m ・ :
d,m.p.258°
H-2),3.20(lH,dd,J=11.4,4Hz,H‐ 3),0,70(H-5),1.35,1.35(2H,H-6)1.26,1.42(2H,H-7),1.52
19),1.20,1.33(2H,H-21),1.56,1.74(2H,H-22),0.96(3H,H-23),0.75(s,3H,H-24),0.89(s,
3H,H-25),0.73(s,3H,H-26),1.H(S,3H,H-27),0.88(s,3H,H-29),0.91(S,3H,H‐ 30);13c_
NMR(CDC13),See Table l.
(2H,H-7),1.882(H-8),1.371(2H,H-11),1.940,1.964(2H,H-12),1.0012,1.727(2草 ,H-1),
s `′
sirο θ「
″ル3‐ ″′θ
ルノ“COpッ sJ″ C,Rf O.63(1:5,
θ「シ White cwstalline compollnd m.p.253°
MeOH:CHC13)
lH― O.985(s,3H,H-23),0,773(s,3H,H-24),0.913(s,
Bα″Jli4`の『 NMR(CDC13,400 MHz)δ
3H,H-25),0.750(s,3H,H-26),1.132(s,3H,H… 27),0.904(s,3H,H-29),0.927(s,3H,H-30),
used as control). Dichloromethane extract showed the least inhibition of 7.14o/oonly (pure
dichloromethanewas used as control).
H3
鉾
♀
C
H
Y
H
,ゝ q ζ
ヽ
C
H
CH2
T へ
11 ) fIH2
Lく CH3
HOM :
Fig. 2 Partial structure of compound 1 solved by HMBC data. Two and three bond C-H
correlationsfrom methyl protonsare shownin bold lines and thosefrom methyleneprotons(H2-
19,H2-28)andmethineprotons(H-8) depictedasalrolv\rs.
ACGC ChemicalResearchCommunicationsVol. 16, 2003 -Page25
]
へ
0
lH Chemicalshift mm COSY
一
三
︲/
〓
〓
︲
33
4 210 dd
4.64)
6/脚 ま
尉:)
13c chemicalshift from 2D‐NMR analyses
r3Cassignments
Fig. 3 lH 1fromCOSY)and of compoundI by 2D-NMR.
ぽ CH3 ヽ
″ノz441(17)
ぼ H20 _
H/z438(100)
ぽ ‐ 2い CH3 _
″ノン423(69)
:a―
r H20 H20ヽ
4/_7420(16)
卜H20 ぽ ‐ 20 H2∝ L
-卜 e 励を40520)
耐 C3H7 H20ヽ
z/z 395(35)
13C-NIr4R,
Table I - Chemical Shift Data (ppm) of compounds 1, 2, 3 and 4
り´
Carbon No. 1 3 4
21 19。
23 29.86 33.75 21.52
31 19.31
Gl 102.63
G2 75.41
G3
G4 71.77
G5 78.55
G6 62.91
ACGC ChemicalResearchCommunicationsVol. 16,2003 -Page27
';
.1
Acknowledgement
We gratefully acknowledge the assistanceof ProfessorDr. R.P. Chaudhary, Cenkal Department
of Botany for the identification of the plant, and Dr. Arjun Hari Banskota, Department of Natural
Product Chemistry, Tomaya Medical and PharmaceuticalUniversity, Japan for providing spectra.
Part of this work was supported by a TWAS research grant (TW NSO joint research project
19197)to Mangala D. Manandhar and M. Iqbal Choudhary; for which the authors are thankful to
TWAS. Thanks are also due to Dean's Office, Tribhuvan University for research grant to
Mangala D. Manandhar.
References
1. of thefloweringplantsof Nepal;A
HaraH., ChaterA.O., WilliamsL.H.J.,An enumeration
Joint project of the British Museum(NaturalHistory) London and University of Tokyo,
Trusteeof the British Museum(NaturalHistory)MansellBook BinderaLimited; London
1982;vol 3, p200.
2. Anjum S., FarooqA., Khan M.R., PraveenJ., ChoudharyM.I.,J..Nat.
Atta-ur-Ratrman,
Prod.,1998;61,202-206.
3. Atta-ur-Rahman,ChaudharyM.I., Khan M.R., ZafaiqbalM, Natural product letter, 1998;
11,81-91.
4. Gewali
Kalouni S.K., ChoudharyM.I., ShaheenF., ManandharM.D., Atta-ur-Rahman,
M.B. andKhalid A, J. Nat.Product,2001;64,842-841.
5
Chang J.K., Yu C.B., Chang D.L., Katalinic J.P. and Block. T.; Indian Journal of
Chemistry,2000; 39(B), 638-642.
9. Banskota A.H.; Cytotoxic and Hepatoprotective Consituent.fro* the Leaves of Combretum
quadrangulare Kurz, 2000; 72.