全 文 ：Chemical Constituents of Euphorbia ebracteolata
SHI Hai-ming and MIN Zhi-da＊
(Department of Natural Medicine Chemistry , China Pharmaceutical University , Nanjing 210009 , China)
Abstract:Aim　To study the chemical constituents of Euphorbia ebracteolata Hayata.Methods　Column chromatography
was used in the isolation procedure , while the structures of isolated compounds were elucidated by spectral data.Results　Six
compounds were isolated and their structures were identified as baccatin(1), 3-acetyl-β-amyrin(2), 3 , 3′-diacetyl-4 , 4′-dim-
ethoxy- 2 , 2′, 6 , 6′-tetrah ydroxy diphenylmethane(3), 2 , 4-dihydroxy-6-methoxy-3-methy l acetophenone(4), β-sitosterol
(5), and daucosterol(6).Conclusion　Baccatin was obtained from Euphorbia ebracteolata for the first time.
Key words:Euphorbia ebracteolata Hayata;chemical constituents;baccatin
CLC number:R284.1;R284.2　　　Document code:A　　　Article ID:1003-1057(2004)3-155-03
Introduction
Euphorbia ebracteolata Hayata (Euphorbiaceae) is
widely distributed in Qingzhou , Shandong Province of
China.This plant is used for the treatment of pulmonary tu-
berculosis and chronic tracheitis
[ 1] .Several diterpene lac-
tones , casbane-type diterpenes , and one isopimarane diter-
pene were isolated from this herb
[ 2-4] .In this paper , we re-
port the isolation and structural elucidation of baccatin(1)
from the roots of Euphorbia ebracteolata Hayata in detail.
Experimental
General
The optical rotations were measured on a Perkin-
Elmer 241 polarimeter.IR spectra were recorded on a
Perkin-Elmer 16 PC FT-IR spectrometer.UV spectra
were obtained on a Beckman DU
®
650 spectrophotometer.
1D and 2D NMR spectra were run on Bruker DRX-500
spectrometers.HRESIMS were obtained on a PE Biosys-
temsMariner System 5140 LC MS spectrometer.Silica gel
(Merck , Kieselgel 60 , 70-230 mesh)was used for col-
umn chromatography.
Plant material
The roots of Euphorbia ebracteolata Hayata were col-
lected from Qingzhou , Shandong Province , China , in
October 1998 , and were identified by Prof.Qin Minjian
(Division of Pharmacognosy , China Pharmaceutical Uni-
Received date:2003-12-23.
＊Corresponding author:Tel 86-25-83220992 ,
E-mail minzd32@sina.com
versity , Nanjing , China).A voucher specimen (No.
98056)was deposited in the herbarium of China Pharma-
ceutical University.
Extraction and isolation
Dried roots of E.ebracteolata(5.0 kg)were milled
and extracted three times with 95%EtOH for 2 h each
time , and the solvent was removed under reduced pres-
sure.The 95%ethanolic extract was suspended in water ,
and was partitioned with petroleum ether , EtOAc and
n-BuOH , successively .The EtOAc-soluble fraction was
concentrated , subjected to silica gel column chromatogra-
phy , and eluted with CHCl3-MeOH(1∶0※2∶1)to yield
6 fractions.Fraction 2 was purified by silica gel column
chromatography [ petroleum ether Me2CO (95∶5)] to af-
ford compound 2.Fraction 3 was purified by repeated sili-
ca gel column chromatography [ petroleum ether Me2CO
(1∶0※7∶3)] to afford compounds 3 , 4 and 5.Fraction 4
was purified by silica gel column chromatography [ petro-
leum ether Me2CO (8∶2)] to afford compound 1.Frac-
tion 5 was purified by silica gel column chromatography
[ CHCl3 CH3OH(10∶1)] to afford compound 6.
Identification
Compound 1　White amorphous powder , [α] 20D -20.0
(c 0.14 , CHCl3), IR(KBr)νmax3 350 (brs), 1 640 ,
1 390 , 1 370 , 895 , 880 cm-1.1H NMR and 13 C NMR
(see Table 1);HRESIMS m z 459.346 4 [ M +H] +
(calculated for C29H47O4459.346 9).
By comparison of their
1
H NMR , 13C NMR and MS
spectra with the data in the references , compounds 2-6
were identified as 3-acetyl-β-amyrin(2)[ 2] , 3 ,3′-diacetyl-
155Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)
Figure 1　Baccatin(1)
4 ,4′-dimethoxy- 2 ,2′,6 ,6′-tetrahydroxy diphenylmethane
(3)[ 5] , 2 , 4-dihydroxy-6-methoxy-3-methyl acetophenone
(4)[ 5] , β-sitosterol(5)[ 6] , and daucosterol(6)[ 6] .
Results and Discussion
Compound 1 was isolated as white amorphous pow-
der.It has a molecular formula C29H46O4 with seven un-
saturated degrees , as deduced from its HRESI mass spec-
trum (m z =459.346 4 [M+H] + , calcd.459.346 9)
and the
1
H and
13
C NMR data.The IR spectrum of 1 in-
dicated the presence of hydroxyl(3 350 cm-1)and dou-
ble bond (1 640 cm-1)groups.The 1H NMR spectrum
of 1(Table 1)showed signals for two olefinic protons(δH
6.63 , d , J =8.9 Hz;δH 6.37 , d , J =8.9 Hz), two
hydroxymethines(δH 3.68 , ddd , J =4.4 , 9.4 , 10.6
Hz;δH 2.94 , d , J =9.4Hz), and seven tertiary meth-
yls(δH 0.97 , s;0.94 , s;0.91 , s;0.88 , s;0.86 , s;
0.85 , s;0.76 , s).The 13C NMR spectrum (Table 1)
gave twenty-nine carbon signals , including seven meth-
yls , eight methylenes , seven methines , and seven quater-
nary carbons.All these data indicated that compound 1 is
a pentacyclic nor-triterpenoid.From this information , in
combination with observed 2D NMR correlations , 1 was
identified as baccatin , which was first found from Sapium
baccatum
[ 7] .Full 1H and 13 C NMR of 1 have been as-
signed for the first time based on its 2D NMR spectra
(HMQC , HMBC).
Table 1　1H NMR(500 MHz)and 13C NMR(125 MHz)spectral data for compound 1(CDCl3 , δJ=Hz)
Position 　　δH δC　 　　HMBC 　　Key NOESY
1α 0.86(m) 46.9(t) C-25, 10 , 5, 2 , 3
1β 2.03(m) C-9 , 5 , 2 , 3 H-2
2 3.68(ddd , J =4.4, 9.4 , 10.6) 69.4(d) CH3-24, 25 , H-1β
3 2.94(d , J=9.4) 84.0(d) C-24, 23 , 2 CH3-23, H-5
4 39.2(s)
5 0.88(m) 56.0(d)
6 1.65(m) 19.3(t)
7 1.55(m) 40.7(t)
8 43.1(s)
9 1.82(m) 51.3(d) C-25 CH3-27
10 39.0(s)
11 1.57(m) 19.0(t)
12α 1.87(m) 49.8(t)
12β 1.84(m)
13 39.8(s)
14 87.4(s)
15 6.63(d , J=8.9) 131.8(d) C-8 , 17 , 14 H-16 , CH3-27
16 6.37(d , J=8.9) 135.3(d) C-22, 17 , 14 H-15 , 22α
17 77.2(s)
18 1.98(m) 40.9(d) C-13, 27 H-19α
19α 1.86(m) 39.2(t) C-18, 17
19β 1.52(m) C-17
20 30.9(s)
21α 1.37(m) 35.2(t)
21β 1.22(m) C-30, 20 , 17
22α 1.50(m) 27.6(t) C-16 CH3-30, 27
22β 1.54(m)
23 0.94(s) 28.2(q) C-24, 3 , 4 , 5
24 0.76(s) 16.1(q) C-23, 3 , 4 , 5 CH3-25
25 0.86(s) 18.4(q) C-10, 5 , 1 CH3-26
26 0.97(s) 18.0(q) C-8 , 14 , 9 CH3-25
27 0.91(s) 24.8(q) C-13, 14 , 12 , 18 H-9
29 0.85(s) 33.0(q) C-30, 20 , 21
30 0.88(s) 23.7(q) C-29, 20 , 21 H-19α
156 Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)
　　The relative stereochemistry of baccatin was assumed
by the Dreiding model in 1977
[ 7] .By a NOESY experiment ,
we can confirm the stereostructural formula of baccatin as
Figure 2.From the NOE correlations between H-2 and CH3-
24 , H-3 and CH3-23 , the configuration of the hydroxyl
groups at C-2 and C-3 were determined to be αand β , re-
spectively.The NOE interactions from CH3-25 to CH3-24
and CH3-26 indicated that these methyl groups are all β-ori-
entated.The NOE correlation between H-9 and CH3-27 re-
vealed that H-9 and CH3-27 are located on the same face
and are α-orientated.The orientation of the peroxide ring
between C-14 and C-17was determined to be β on the basis
of the NOE interactions between CH3-27 and H-15.
Figure 2　Key NOE correlations of compound 1
References
[ 1] Jiangsu College of New Medicine.A Dictionary of the Tradi-
tional Chinese Medicines [ M] .Shanghai:Shanghai Science and
Technology Press , 1986.1898-1900.
[ 2] Wang WX , Ding XB.Studies on diterpenoids from the roots of
Euphorbia ebracteolata [ J] .Acta Pharm Sin , 1998 , 33(2):
128-131.
[ 3] Xu ZH , Sun J , Xu RS , et al.Casbane diterpenoids from Eu-
phorbia ebracteolata [ J] .Phytochemistry , 1998 , 49(1):149-
151.
[ 4] Xu ZH , Qin GW , Xu RS.An isopimarane diterpene from Eu-
phorbia ebracteolata Hayata [ J] .J Asian Nat Prod Res , 2000 ,
2(4):257-261.
[ 5] Wang WX , Ding XB.Acetophenone derivertives from Euphor-
bia ebracteolata Hayata [ J] .Acta Pharm Sin , 1999 , 34(7):
514-517.
[ 6] Wang WX , Ding XB.Studies on the chemical constituents of
Yuexiandaji(Euphorbia ebracteolata)[ J] .Chin Tradit Herb
Drugs , 1999 , 30(1):1-3.
[ 7] Saha B , Naskar DB , Misra DR , et al.Baccatin , a novel nor-
triterpene peroxide isolated from Sapium baccatum Roxb.[ J] .
Tetrahedron Lett , 1977 , 35:3095-3098.
月腺大戟的化学成分
史海明 , 闵知大
(中国药科大学天然药化教研室 , 江苏南京 210009)
摘要:目的　研究月腺大戟的化学成分 。方法　运用柱层析进行分离 ,并对所分得的化合物运用波谱数据进行了结构解
析。结果　从月腺大戟中分离得到 6个化合物并鉴定了其结构 ,分别为:baccatin(1), 3-乙酰-β 香树酯醇(2), 3 , 3′-二乙酰基-
4 , 4′-二甲氧基-2 , 2′, 6 , 6′-四羟基二苯甲烷(3), 2 , 4-二羟基-6-甲氧基-3-甲基苯乙酮(4), β-谷甾醇(5), 胡萝卜苷(6)。结论　
baccatin为首次从月腺大戟中分离得到。
关键词:月腺大戟;化学成分;baccatin
157Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)