全 文 ：　　　　 天然产物研究与开发　 　　　　　
2003　Vo1.15　No.6 NATU RAL PRODUCT RESEARCH AND DEVELOPMENT　 　　　　　　　　　　
　
　
　
　
　　收稿日期:2003-01-20　　　修回日期:2003-05-20
Project supported by the f inancial support f rom the State Key
Laboratory of Phytochemist ry and Plan t Resources in West Chi-
na , Kunming Insti tute of Botany , Chinese Academy of Sciences ,
and supported by the Knowledge Innovation Project from the
North West Plateat Inst itu te of Biology , Chinese Academy of S ci-
ences(No.CXLY-2002-7).
＊ Author for correspondence.Tel:86-871-5223421;E-mail:
xdluo@mail.kib.ac.cn
CHEMICAL CONSTITUENTS FROM
EUPHORBIA WALLICHII
WANG Huan
1 , 2 ,ZHANG Xiao-feng1 ,PAN Li1 ,
YANG Shu-min2 ,MA Yun-bao2 , LUO Xiao-dong2＊
(1.North West Plateau Institute of Biology , Chinese Academy of Sciences , Xining Qinghai　810001 , China;
2.S tate Key Laboratory of Phytochemistry and Plant Resources in West China , Kunming Institute of Botany ,
Chinese Academy of Sciences , Kunming　650204 , China)
Abstract　Eleven know n compounds were isolated from the roots of Euphorbia wallichii for the first time.
They w ere elucidated to be three triterpenoids , β-amyrin (1), β-amyrin acetate(2)and 3β-aceto xy-lupenol
(3), one no r-triterpene pero xide baccatin (4), two caffeic esters (5a , 5b), palmitic acid-2 , 3-dihydroxy-
propanenyl ester(6), palmitic acid(7), scopoletin(8), β-sitosterol(9)and daucosterol(10)on the basis of
spectral methods.Among them , compound 5a , 5b were repor ted firstly in the spurge family.And the NMR
assignments of compounds 5a and 5b were giv en for the first time.
Keywords　Euphorbia wallichii;Euphorbia;baccatin;caffeic ester;palmitic acid-2 , 3-dihydro xy-propa-
nenyl ester
The genus Euphorbia is the largest in the spurge
family , comprising about 2000 species.More than 80
of them are distributed in China.Various groups[ 1 ～ 3]
had been wo rking on the chemical constituents of this
genus , finding many biologically active diterpenes.
Euphorbia wal lichi i , a t raditional medicinal plant ,
mainly distributed in Qinghai province , Tibet and
Yunnan province of China , has been used by Tibetan
of China to cure furuncle , exanthema and cutaneous
anthrax.To make full use of this plant , we studied
i ts chemical constituents.From the alcohol ext ract of
the roots of this plant , we have obtained three t riter-
penoids , β-amy rin (1[ 4] ), β-amy rin acetate (2[ 4] )
and 3β-acetoxy-lupenol (3[ 5] ), one nor-triterpene
pero xide baccatin (4[ 6]), two caffeic esters (5a[ 7] ,
5b[ 7]), palmit ic acid-2 , 3-dihydroxy-propanenyl ester
(6[ 8]), palmitic acid(7[ 9]), scopoletin(8), β- si tos-
terol(9)and daucosterol (10).In many reports[ 10] ,
4 was used as material to synthesize drugs.And 5a
and 5b were seldom reported.In this paper , we de-
scribe the isolation and st ructure elucidation of these
compounds.
1　Results and discussion
Compound 4 gave a molecular formula C29H46O4 by
EIMS and 13C NMR spect rum.The 1H NMR spec-
t rum showed signals at δ0.80 ～ 1.01 (7-tertiary
CH3), 3.04(1H , d , 9.4 Hz), 3.78(1H ,m), 6.42
(1H , d , 9.0 Hz), and 6.68 (1H , d , 9.0 Hz),
which w as very similar to that of Baccatin[ 6] .Thus 4
was assumed to be Baccatin , suppo rted by the HMQC
and HMBC spect ra(see table 1).And the 13C NMR
data w ere given (see table 2).
483
DOI :10.16333/j.1001-6880.2003.06.001
Table 1　The key cor relations of HMQC and HMBC fo r com-
pound 4(500 MHz , CDCl3)
Position δH δC HMBC
1 2.08;0.91 46.7 C-2 , C-3 , C-5 , C-10
3 3.04 83.9 C-1 , C-2 , C-4 , C-23 , C-24
9 1.86 51.2 C-1 , C-8 , C-10 , C-26
12 2.04 41.0 C-11 , C-27
15 6.68 131.8 C-8 , C-13 , C-14 , C-17
16 6.42 135.2 C-14 , C-17 , C-18 , C-22
19 1.30;0.65 40.6 C-17 , C-18 , C-20 , C-21 , C-29
21 1.43;1.31 35.1 C-17 , C-20 , C-22 , C-29
22 1.60 27.5 C-16 , C-17 , C-20 , C-21
23 0.99 28.2 C-3 , C-4 , C-5 , C-24
24 0.80 16.0 C-3 , C-4 , C-5 , C-23
25 0.89 18.4 C-1 , C-2 , C-5 , C-9 , C-10
26 1.01 18.0 C-8 , C-9 , C-14
27 0.95 24.8 C-13 , C-14 , C-18
Table 2 　13C-NM R spectral data fo r compounds 2 ～ 4(100
MHz , CDCl3)
C 2 3 4
1 38.2(t) 38.4(t) 46.7(t )
2 23.7(t) 23.7(t) 69.3(d)
3 80.9(d) 81.0(d) 83.9(d)
4 37.7(s) 37.8(s) 39.2(s)
5 55.2(d) 55.4(d) 55.9(d)
6 18.2(t) 18.2(t) 19.0(t )
7 32.6(t) 34.2(t) 39.0(t )
8 39.8(s) 40.9(s) 43.0(s)
9 47.5(d) 50.3(d) 51.2(d)
10 36.8(s) 37.1(s) 38.9(s)
11 23.5(t) 20.9(t) 19.3(t )
12 121.6(d) 25.1(t) 41.0(t )
13 145.2(s) 38.0(d) 39.7(s)
14 41.7(s) 42.8(s) 87.4(s)
15 28.4(t) 27.4(t) 131.8(d)
16 26.1(t) 35.6(t) 135.2(d)
17 32.5(s) 43.0(s) 77.2(s)
18 47.2(d) 48.3(d) 49.7(d)
19 46.8(t) 48.0(d) 40.6(t )
20 31.1(s) 150.9(s) 30.8(s)
21 34.7(t) 29.8(t) 35.1(t )
22 37.1(t) 40.0(t) 27.5(t )
23 28.0(q) 27.9(q) 28.2(q)
24 16.7(q) 16.5(q) 16.0(q)
25 15.5(q) 16.2(q) 18.4(q)
26 16.8(q) 16.0(q) 18.0(q)
27 25.9(q) 14.5(q) 24.8(q)
28 26.9(q) 18.0(q) 32.9(q)
29 33.3(q) 109.3(t) 23.7(q)
30 23.6(q) 19.3(q)
31 171.0(s) 171.0(s)
32 21.3(q) 21.3(q)
Compound 5a ,5b were isolated as a mixture.The 1H
NMR of 5 show ed signals for a typical ABX spin sy s-
tem at δ6.61 (1H , d , 8.2 Hz), 6.72 (1H , dd ,
8.2 Hz , 2.1 Hz)and 6.93 (1H , d , 2.1 Hz), indi-
cating the presence of three protons w ith ortho , or-
tho/meta and meta coupling , respect ively.A trans
double bond w as presented by signals at δ6.05 and
7.34 ppm with a coupling constant of J =15.9 Hz.
It also showed signals for a methyl (δ0.68 , t , 7.0
Hz), a methylene (δ1.47 , m)and numbers of
methylenes at δ1.05 ppm. The above 1H NMR
spectra were ident ical to those of caf feic ester in refer-
ence.So i t w as established as a caffeic ester , which
w as confi rmed by HMQC and HMBC spectra.Fur-
thermore , the EIMS spect rum showed two molecular
weight at m/ z 460(28)and 432(68).Hence 5 was
a mixure of Caffeic acid eicosyl ester(5a , C29H 48O4)
and Caffeic acid octadecyl ester(5b , C27H 44O4).Ac-
cording to the relative intensiti tes of the molecular
ions , i t w as estimated by the method of ref.[ 11] that
5a and 5b were present in the approximate ratio 1∶
2.4.
2　Experimental
2.1　Apparatus and Plant materials
MS spect ra w ere obtained wi th a VG Auto Spec-3000
spect rometer , at 70 eV fo r EI.1D and 2D-NMR
spect ra were recorded on a Bruker AM-400 and a
DRX-500 MHz spect rometer wi th TMS as internal
standard.And Silica gel (200 ～ 300 mesh)for CC
and GF254 for analytical TLC were f rom the Qingdao
M arine Chemical Factory , P.R.China.Euphorbia
484　　　　　　　　　 天然产物研究与开发 2003　Vo1.15　No.6
wallichii was collected f rom Xinghai county , Qinghai
province, China , in July 2001.It w as identified by
Prof.ZHANG Xiao-feng , Northwest Plateau Insti-
tute of Biology , Academia Sinica , Xining , Qinghai ,
P.R.China , where a voucher specimen (No.1002)
was deposi ted.
2.2　Extraction and Isolation
Air-dried roo ts (10 kg)were ext racted w ith EtOH
(95%)for four times.After removal of the solvent
by evapo ration , the residues were suspended in H2O
and ex t racted wi th CHCl3 for three times.The CHCl3
fraction w as concentrated in vacuo to give 100 g of
the residue.The residue w as separated repeatedly by
chromatography on silica gel column and RP-18 to af-
ford 1(46 mg), 2(3691 mg), 3(16 mg), 4(30 mg),
5(20 mg), 6(10 mg), 7(20 mg), 8(90 mg), 9(500
mg), and 10(102 mg).
3　Indentification
β-Amyrin (1)　C30H50O , colorless needles;EIMS
m/z 426 [ M] +(49), 411 (15), 257 (12), 247
(11), 229(11), 218(100), 203(68), 189(51),
176 (29), 161 (28), 147 (32), 135 (57), 121
(49), 109 (58), 95 (68), 81 (57), 69 (64), 55
(50).These data w ere identical w ith those of β-
amy rin[ 4] , and its TLC w as identical wi th an authen-
tic sample.
β-Amyrin acetate(2)　C32H52O2 , colorless needles;
1H-NMR(CDCl3):δ5.15(1H , t , 3.4 Hz , H-12),
4.47(1H , m , H-3), 2.01 (3H , s , H-32);13C-
NMR(CDCl3)see table 2;EIM S m/ z 468 [ M] +
(22), 453(6), 257 (6), 229(3), 218(100), 203
(55), 189(25), 135(27), 121(28), 107(39), 95
(38), 81(36), 69(54), 55(36).These data were
identical with those of β-amy rin acetate[ 4] .
3β-Acetoxy-lupenol (3)　 C32H52O2 , colorless nee-
dles;1H-NMR(CDCl3):δ4.66(1H , d , 2.0 Hz , H-
29′), 4.55 (1H , d , 2.0 Hz , H-29), 4.50 (1H ,
dd , 7.2 , 13.0 Hz , H-3), 2.02 (3H , s , H-32),
1.66(3H , s , H-30);13C-NMR(CDCl3)see table
2;EIM S m/ z 466 [M-2H] +(100), 451(29), 406
(24), 391 (18), 355 (32), 296 (18), 274 (20),
247 (32), 227 (18), 217 (53), 202 (50), 188
(82), 174 (38), 160 (39), 146 (42), 135 (56),
120(57), 108 (55), 94 (56), 80 (52), 68(51),
54(47).These data were identical w ith those of 3β-
acetoxy-lupenol[ 5].
Baccatin (4)　C29 H46 O4 , colorless needles;1H-
NMR(CDCl3):δ0.91 , 2.08 (2H , m , H-1), 3.78
(1H , m , H-2), 3.04(1H , d , 9.4 Hz , H-3), 0.92
(1H , m , H-5), 1.61 (2H , m , H-6), 1.92 (2H ,
m , H-7), 1.86 (1H , m , H-9), 1.70(2H , m , H-
11), 2.04(2H , m , H-12), 6.68 (1H , d , 9.0 Hz ,
H-15), 6.42 (1H , d , 9.0 Hz , H-16), 1.91 (1H ,
m ,H-18), 0.65 , 1.30(2H , m , H-19), 1.31 , 1.43
(2H , m , H-21), 1.60(2H , m , H-22), 0.99(3H ,
s , H-23), 0.80 (3H , s , H-24), 0.89 (3H , s , H-
25), 1.01 (3H , s , H-26), 0.95 (3H , s , H-27),
0.90(3H , s , H-28), 0.93 (3H , s , H-29);13C-
NMR(CDCl3)see table 2;EIM S m/ z 458[ M] +
(19), 443 (17), 426 (36), 308 (37), 291 (28),
221 (20), 208 (94), 191 (70), 177 (86), 163
(46), 151(51), 135(46), 121(81), 109(96), 95
(75), 81 (71), 69 (97), 55 (100).These data
were identical wi th those of baccatin[ 6].
Caffeic acid eicosyl ester(5a)(C29H48O4)and caffe-
ic acid octadecyl ester (5b)(C27H44 O4)　White
pow ders;1H-NMR(Me3OD):δ7.34 (1H , d , 15.9
Hz , H-7), 6.93(1H , d , 2.1 Hz , H-2), 6.72(1H ,
dd , 8.2 , 2.1 Hz , H-6), 6.61(1H , d , 8.2 Hz , H-
5), 6.05 (1H , d , 15.9 Hz , H-8), 3.94 (2H , t ,
6.7 Hz , H-1′), 1.47(2H , m , H-2′), 1.05(br s ,
H-3′～ H-n′), 0.68 (3H , t , 7.0 Hz , Me);13C-
NMR (Me3OD):δ127.6(C-1), 115.2 (C-2),
146.9 (C-3), 146.9 (C-4), 116.5 (C-5), 122.9
(C-6), 146.7 (C-7), 115.2 (C-8), 169.2 (C-9),
65.5 (C-1′), 29.8 (C-2′), 27.1 (C-3′), 30.4 ～
30.7(C-4′～ C-(n-2)′), 33.1(C-(n-1)′), 23.7(C-
n′), 14.5 (Me);EIM S m/ z 460 ([ M ] + of 5a)
(28), 432 ([ M ] + of 5b)(68), 180 (100), 163
(71), 136(38), 123(20), 97 (12), 89 (13), 83
(18), 69(26), 57(41), 55(39).These data w ere
identical w ith those of caf feic esters [ 7].
Palmitic acid-2 , 3-dihydroxy-propanenyl ester (6)　
C19 H38 O4 , white pow ders;1H-NMR (CDCl3):δ
4.19(2H , m , H-1′), 3.93 (1H , m , H-2′), 3.64
4852003　Vo1.15　No.6 王　环等:大果大戟的化学成分 　　　　　　　　　
(2H , m , H-3′), 2.33(2H , t , 7.6 Hz , H-2), 1.60
(2H , m , H-3), 1.24 (24H , br s , H-4 ～ H-15),
0.85(3H , t , 6.7 Hz , H-16);13C-NMR(CDCl3):
δ65.1 (C-1′), 70.2 (C-2′), 63.3 (C-3′), 174.4
(C-1), 34.1(C-2), 24.9(C-3), 29.1 ～ 29.7 (C-4
～ C-13), 31.9 (C-14), 22.7 (C-15), 14.1 (C-
16);EIMS m / z 299 [ M-H] +(39), 270(21), 257
(48), 239(100), 134(70), 112(38), 98(94), 84
(58), 74 (60), 57(49).These data w ere identical
w ith those of reference
[ 8].
Palmitic acid(7)　C16H32O2 , whi te pow ders;EIMS
m/ z 256 [ M] +(53), 239(4), 221(4), 213(9),
196(14), 185(22), 171(13), 165(5), 157(10),
140(7), 129(100), 115(23), 99(24), 85(21),
73(57), 60(33), 57(50).These data w ere identi-
cal w ith those of reference[ 9].
Scopoletin(8), β-sitosterol (9)and daucosterol (10)
were respectively indentified by TLC with authentic
samples.
References
1　 JIA Zhongjian , DING Yili.New diterpenoids from Eu-
phorbia sieboldiana.Planta Med , 1991 , 57:569～ 571
2　 Appendino G , Jakupovic S , T ron GC , et al.Macrocyclic
diterpenoids from Euphorbia semiperfoliata.J Nat Prod ,
1998 , 61:749 ～ 756
3　 Sutthivaiyakit S , Thapsut M , Prachayasittikul V.Con-
stituents and bioactivity of the tubers of Euphorbia sessil-
if lora.Phytochemistry , 2000 , 53:947 ～ 950
4　 ZHONG Haijun , LUO Shide , WANG Huiying , et al.
Chemical constituents of Crepis phoeni x. Acta Botanica
Y unnanica , 1999 , 21:531 ～ 534
5　 Sholichin M , Yamasaki K , Kasai R , et al.13C Nuclear
magnetic resonance of lupane— type triterpenes , lupeol , be-
tulin and betulinic acid.Chem Pharm Bull , 1980 , 28:
1006 ～ 1008
6　 Saha B , Naskar DB , Misra DR , et al.Baccatin , a novel
no r-triterpene peroxide isola ted from Sapium Baccatum
roxb.Tetrahedron Letters , 1977 , 35:3095 ～ 3098
7　 Iinuma M , Ohyama M , Tanaka T , et al.Five flavonoid
compounds from Echinosophora Koreensis.Phytochemis-
try , 1993 , 33:1241 ～ 1245
8　 ZHANG Ke , NI Wei , CHEN Chang-xiang.The con-
stituents of Piper boehmeriaefolium var.tonkinense.
Natural Product Research and Development , 1999 , 11
(1):44 ～ 47
9　 CAO Zhi-mao , LIU Jing-ming.Chemical constituents of
Trichosanthes rosthornii Harms.China Journal of Chinese
Material Medica , 1991 , 16:97 ～ 99
10　Gosw ami A , Khastgir HN.Indian J Chem , Sect. B ,
1980 , 19B(4):315 ～ 316
11　Martinez V , Barbera O , Parareda J S , et al.Phenolic and
acetylenic metabolites from Artemisia assoana.Phy to-
chemistry , 1987 , 26(9):2619 ～ 2624
大果大戟的化学成分
王　环1 , 2 　张晓峰1 　潘　莉1 　杨淑敏2　马云保2　罗晓东2＊
(1.中国科学院西北高原生物研究所　青海 西宁　810001;
2.中国科学院昆明植物研究所 植物化学与西部植物资源持续利用国家重点实验室　云南 昆明　650204)
摘　要　从大果大戟的根部首次分离得到 11 个化合物。利用波谱方法鉴定为 β-香树素(1), β-香树素乙
酸酯(2), 3β-乙酰化羽扇豆烯醇(3), baccatin(4), 2 个 caffeic esters(5a , 5b),棕榈酸-1-甘油酯(6),棕榈酸
(7),东莨菪内酯(8),β-谷甾醇(9)和胡萝卜甙(10)。其中 5a , 5b是第一次在大戟属中得到;并对 5a , 5b
的碳谱和氢谱数据进行了全归属。
关键词　大果大戟;大戟属;baccatin;caffeic ester;棕榈酸-1-甘油酯
486　　　　　　　　　 天然产物研究与开发 2003　Vo1.15　No.6