全 文 ：　　　　 天然产物研究与开发　 　　　　　
　　　　　　　　　　 NAT URAL PRODUCT RESEARCH AND DEVELOPMENT　 2004　Vol.16　No.6
　
　
　
　
　　Received 20 M ay 2004;Accepted 3 September 2004
　　Foundation Item:The Natural Science Foundation of Yunnan Provincial
Education Department(No.02ZY018);Natural Science Foundation of
Yunnan University(No.2003Q010A)
　＊Corresponding author　E-mail:liliang5758@sina.com
THE CHEMICAL STUDY ON CLEIDION
BREVIPETIOLATUM
LI Cui-hong1 ,ZHOU Hong-jiao2 ,YANG Xiao-dong1 ,ZHAO Jing-feng1 , LI Liang1＊
(1.School of Pharmacy , Yunnan University , Kunming　650091 , China;
2.Rong-Jun Hospital of Yunnan , Kunming　650214 , China)
Abstract　Six compounds were isolated from the ethanol extract of Cleidion brevipetiolatum for the first time.The
compounds were identified as benzy l-1-O-β-D-glucopyranoside(1), chavicol-1-O-β-D-glucopy ranoside(2), 3 , 4 , 5-
trimethoxyphenol(3), 3 , 4 , 5-trimethoxyphenol-1-O-β-D-g lucopy ranoside(4), β-sitosterol(5), daucosterol(6).
Key words　Eupho rbiaceae;Cleidion brevipetiolatum ;glucoside
棒柄花的化学成分研究
李翠红1 　周红娇2 　羊晓东1 　赵静锋1 　李　良1＊
(1.云南大学药学院　昆明　650091;2.云南省荣军医院　昆明　650214)
摘　要　从棒柄花(Cleidion brev ipetiolatum)的乙醇提取物中分离得到 6 个化合物 , 经波谱分析确定其结构
为:benzy l-1-O-β-D-glucopyranoside(1), chavicol-1-O-β-D-glucopy ranoside(2), 3 , 4 , 5-trimethoxypheno l(3), 3 , 4 , 5-
trimethoxyphenol-1-O-β-D-glucopyranoside(4), β-sitosterol(5), daucosterol(6),以上化合物均为首次从该植物中
分离得到。
关键词　大戟科;棒柄花;糖苷
The genus Cleidion(Euphorbiaceae)is represented by only
3 species in China.C.brevipetiolatum , C.javanicum
and C.bracteosum are distributed in the southwestern
part of the country at an altitude of 200 ～ 1500 meters[ 1] .
They are used in folk medicine for t reatment of inflamma-
tion , diuresis , acute and chronic hepatitis , and possess
detoxic effect[ 2] .To the best of our knowledge , no phyto-
chemical study on Cleidion brevipetiolatum has hitherto
been reported.In our research , six compounds , benzyl-1-
O-β-D-glucopyranoside(1), chavicol-1-O-β-D-glucopyra-
noside(2), 3 , 4 , 5-trimethoxyphenol (3), 3 , 4 , 5-
trimethoxyphenol-1-O-β-D-glucopyranoside(4), β-sitos-
terol(5)and daucosterol(6), were isolated for the first
time.Their structures were determined on the basis of
spect ral data.
Experimental
General experimental procedures
Kofler melting point were uncorrected.UV(in MeOH)and
IR spectra(KBr disc)were measured on Shimadzu UV-
210A and IR-450 spectrophotometer , respectively.NMR
were obtained on a Brucker AM-300 spect rometer using
TMS as internal standards.A VG AutoSpec-3000 spec-
t rometer was used to record MS spect ra(70 eV).Silica gel
(100 ～ 300 mesh)f rom Qingdao Haiyang Chemical Facto-
ry were used for column chromatography.All solvents
were industrial products , and distilled before using.
Plant material
The whole plants were collected in Xishuangbanna of
514
DOI :10.16333/j.1001-6880.2004.06.007
Yunnan Province , in September 2003 , and ident if ied
as Cleidion brev ipetiolatum by Prof.HU Zhi-hao.A
voucher specimen(No.03-L-001)was deposi ted in the
Department of Phy tochemist ry ,School of Pharmacy ,
Yunnan University .
Extraction and isolation
The dried and powdered whole plants(8.0 kg)were
soaked with 95% EtOH(10 L ×4)at room temper-
ature each 2 days.The combined ex tract was then
concentrated in vacuo.The residue w as suspended in
H2O , and ext racted w ith EtOAc(5 L ×3)and n-
BuOH(5 L ×3), respectively.The n-BuOH fraction
(60.0 g)was subjected to silica gel column(1 kg ,100
～ 200 mesh), eluted with CHCl3-CH3OH(30∶1-0∶1)
to give 15 fractions.Fractions 1-3 w ere purified on
silica gel column using CHCl3-Me2CO(10∶1- 0∶1)as
solvents to yield compounds 1(100 mg),2(56 mg), 3
(66 mg), 4(17 mg),5(1.0 g)and 6(90 mg).
Identification
Benzyl-1-O-β-D-glucopyranoside(1)
Colorless oil ,C13H18O6.[ α] 25D-50.1°(MeOH , c 1.05), IR
νmax cm-1 :3260 , 1660 , 1390 , 1380 , 1080 , 1040.MS m/
z :271(M +1)+ , 253 , 209 , 163 , 143 , 108 , 91.1H NMR
(300 MHz ,CD3OD):δ7.54(2H ,d , J =7.5 Hz ,H-6 ,H-
2), 7.49(3H , m , H-3 , H-4 , H-5), 4.99(2H , s , H-7),
5.09(1H , d , J =6.0 Hz ,Glu:H-1).13C NMR(75 MHz ,
CD3OD ,DEPT):δ137.2(s ,C-1), 127.5(d ,C-2 ,C-6),
127.4(d ,C-3 ,C-5), 126.9(d ,C-4), 69.9(t ,C-7), 101.4
(d , Glu:C-1′), 76.1(d , Glu:C-2), 76.0(d , Glu:C-3),
73.2(d ,Glu:C-4), 69.7(d , Glu:C-5), 60.9(t , Glu:C-
6).These data were identical with those of benzyl-1-O-β-
D-glucopyranoside[ 3].
Chavicol-1-O-β-D-glucopyranoside(2)
Amorphous powder , C15H20O 6 , [ α] 20D-53.1°(MeOH , c
0.65),UV λmax nm:253 , 271 , 280.1H NM R(300 MHz ,
CD3OD):δ7.12(2H , dd , J =7.8 , 2.1 Hz , H-2 ,H-6),
7.02(2H , dd , J =7.8 , 2.0 Hz ,H-3 ,H-5), 5.96(H , m ,
H-8), 5.42(1H , d , J=7.6 Hz ,Glu:H-1), 5.01(2H , d , J
=12.7 Hz , H-9), 3.74(2H , d , J =6.6 Hz , H-7), 13C
NMR(75 MHz , CD3OD , DEPT):δ157.8(s , C-1),
139.5(d ,C-2 ,C-6), 130.9(d ,C-3 ,C-5), 130.7(s , C-4),
40.7(t ,C-7), 118.2(d ,C-8), 116.1(t , C-9), 102.9(d ,
Glu:C-1), 78.4(d ,Glu:C-2), 78.3(d , Glu:C-3), 75.8
(d , Glu:C-4), 75.3(d , Glu:C-5), 62.9(t ,Glu:C-6).
These dat a were identical with those of chavicol-1-O-β-D-
glucopy-ranoside[ 4] .
3 ,4 ,5-Trimethoxyphenol(3)
White pow der ,C9H12O4 , IRνmax cm-1:3440 , 1598 , 1510 ,
1
H NMR(300 MHz , CDCl3):δ6.50(2H , s , aromatic
H), 5.09(1H , s ,-OH), 3.80(each 3H , s , 3-OCH3 , 5-
OCH3), 3.70(3H , s , 4-OCH3), 13C NMR(75 MHz , CD-
Cl3 ,DEPT):δ156.2(s ,C-1), 98.0(d ,C-2 , 6), 142 , 6(s ,
C-3 , 5), 133.3(s ,C-4), 56.4(q , 3-OCH3 , 5-OCH3), 57.2(q , 4-OCH3).These data were identical with those of 3 ,
4 , 5-trimethoxyphenol[ 5].
3 ,4 ,5-Trimethoxyphenol-1-O-β-D-glucopyranoside(4)
White needles ,C15H22O9 ,mp.201 ～ 203 ℃, [α] 20D-22.3°(MeOH , c 0.38), IR νmax cm-1 :3410 , 2910 , 1650 ,
1075.EIMS m/ z :346(M)+ , 184 , 169 , 84.1H NMR
(300 MHz , CD3OD):δ6.48(2H , s ,H-2 , 6), 4.80(1H ,
d , J =7.0 Hz , Glu:H-1), 3.69(3H , s , 4-OCH3), 3.25(each 3H , s , 3-OCH3 , 5-OCH3), 13C NM R(75 MHz ,
CD3OD ,DEPT):δ157.0(s , C-1), 96.4(d , C-2 , C-6),
153.3(s ,C-3 ,C-5), 143.6(s ,C-4), 103.3(d ,Glu:C-1),
78.8(d , Glu:C-2), 72.8(d , Glu:C-3), 71.8(d , Glu:C-
4), 71.5(d , Glu:C-5), 61.9(t , Glu:C-6), 56.4(q , 3-
OCH3 , 5-OCH3), 60.9(q , 4-OCH3).These data were i-
dentical with those of 3 , 4 , 5-trimethoxyl-phenyl-1-O-β-
D-glucopyranoside[ 6].
β-Sitosterol(5)
Colorless needles(CHCl3), mp.136 ～ 137 ℃.IR νmax
cm-1 :3500 , 2930 , 1470 , 1380 , 1065 , 960.EIMS m/ z :
414(M +), 396 , 381 , 329 , 303 , 273 , 255 , 213 , 43.Melting
point , IR , TLC behavior were identical with those of an
authentic sample.
Daucosterol(6)
White amorphous powder.mp.304 ～ 305 ℃ .IR νmax
cm-1 :3400 , 2960 , 2850 , 1450 , 1375 , 1360 , 1160 , 1100 ,
1025.IR , TLC behavior were identical with those of an
authentic sample.
References
1　 Institute of Botany.The Chinese Academy of Sciences , F lo-
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Science Press , 1996.74-75
2　 Xie ZW , Yu YC.I ndex Chinese T raditional and Herbal
Drugs , Beijing:People s Medical Publishing House , 1989.
371
3　 Hide I , Yoshiaki O , Akira I , et al.Phenolic plant g row th
inhibitors from the flowers of Cucurbita pepo.Phyto-
chemistry , 1982 , 21(8):1935-1937
4　 Ryuichi H , Dervilla MXD.Glycoside from Pinus contorta
needles.Phy tochemistry , 1977 , 16:1587-1590
5　 Mclean S , Murrary DG.Constituents o f Nauclea diderr-
ichii IV.miscellaneous substance biogenetic conside-
rations.Can J Chem , 1972 , 50(10):1496-501
6　 Hiroko S , Yutaka S , Motomu O , et al.Phenolic glucoside
from Parabenzoic praecox.Phytochemistry , 1988 , 27(2):
644-646
5152004　Vol.16　No.6 李翠红等:棒柄花的化学成分研究