全 文 ： 2010 年 3 月 第 8 卷 第 2 期 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 81

Chinese Journal of Natural Medicines 2010, 8(2): 0081−0083
doi: 10.3724/SP.J.1009.2009.00081
Chinese
Journal of
Natural
Medicines







• Original Papers •
A New Jatrophane Diterpenoid from Euphorbia peplus
SONG Zhi-Qin1, 2, MU Shu-Zhen1, DI Ying-Tong3, HAO Xiao-Jiang1, 3*
1The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guiyang 550002;
2Guiyang College of Traditional Chinese Medicine, Guiyang 550002;
3State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences,
Kunming 650204, China
Available online Mar. 2010
[ABSTRACT] AIM: To study the chemical constituents of Euphorbia peplus. METHODS: Compounds 1-3 were isolated and puri-
fied by silica gel column chromatography, MCI and Sephadex LH-20. Their structures were mainly elucidated by spectroscopic analy-
sis and physicochemical characteristics. RESULTS: Three compounds were identified as euphopeplin A (1), 2α, 5α, 7β, 8α, 9α,
14β-hexaacetoxy-3β-benzoyloxy-15-hydroxyjatropha-6 (17), 11E-diene (2) and 5α, 8α, 9β, 10β, 14α-pentaacetoxy-3β-benzoy-loxy-
15-hydroxypepluane (3). CONCLUSION: A new jatrophane diterpenoid, euphopeplin A (1) was isolated from Euphorbia peplus.
[KEY WORDS] Euphorbiaceae; Euphorbia; Euphorbia peplus; Diterpenoids; Jatrophane diterpenoids
[CLC Number] R284.1 [Document code] A [Article ID]1672-3651(2010)02-0081-03

1 Introduction
The widespread plants of the genus Euphorbia (Euphor-
biaceae) are much richer in biologically active diterpenoids
with diverse structures [1]. Besides the well-known skin irri-
tant and tumour-promoting tigliane, ingenane and daphnane
diterpenoids, the chemical diversity and therapeutically rele-
vant bioactivities of the chemical constituents [2-3] have recen-
tly attracted considerable attentions to macrocyclic diterpe-
noids. Euphorbia peplus Linn. is originally native to Europe
and North Africa. Previous studies on the chemical constitu-
ents of E. peplus was focused on the foreign species [4-5], and
those of Chinese E. peplus have not been investi- gated before.
Aiming to find new and potentially bioactive diterpenoids
from this species, we investigated the chemical constituents of
E. peplus grown in China, and obtained a new jatrophane
diterpenoid (1) and two known diterpenoids (2) and (3).
2 Experimental
2.1 General
Optical rotation was measured on a Horiba SEPA-300

[Received on] 23-Apr-2009
[Research Funding] This project was supported by the Specialized
Foundation for Talents of Guizhou Province (No. 2008114), Special-
ized Foundation for Modernization of Traditional Chinese Medicine
of Guizhou Province (No. 20065041) and the Ministry of Science
and Technology (No. 2007CB516813).
[*Corresponding author] HAO Xiao-Jiang: Prof., Tel: 86-851-
3804492, E-mail: haoxj@mail.kib.ac.cn
high sensitivity polarimeter digital polarimeter. IR (KBr)
spectra were recorded on a Bio-Rad FTS-135 spectrometer.
1D- and 2D-NMR spectra were obtained on an INOVA-400
MHz NMR spectrometer with TMS as an internal standard.
ESI-MS spectra were carried on a Waters 2695 HPLC-
Thermo Finnigan LCQ Advantage ion trap mass spectrometer.
HR-ESI-MS spectrum was measured by VG Auto Spec 3000
spectrometer. Column chromatography was performed on
silica gel (200-300 mesh and H-60, Qingdao Marine Chemi-
cal Company, Qingdao, China), MCI gel (75-150 μm; Mitsu-
bishi Chemical Corporation, Tokyo, Japan), Sephadex LH-20
(40-70 μm, Amersham Pharmacia Biotech AB, Uppsala,
Sweden). Solvents used for extraction and isolation were
distilled prior to use. Spots of TLC were detected by spraying
with 5% H2SO4 followed by heating.
2.2 Plant Material
The whole plant of E. peplus was collected from Kun-
ming Botanical Garden, Yunnan Province, China in October
2007. The specimen was identified by Prof. Gong Xun,
Kunming Institute of Botany, Chinese Academy Sciences.
2.3 Extraction and Isolation
The air-dried and powered whole plant of Epeplus (9.5
kg) was extracted with 95% EtOH under reflux four times.
The crude extract was concentrated in vacuo, and then parti-
tioned between petroleum ether and H2O. Evaporation of
the organic phase gave a residue (299 g), which was chro-
matographed on a silica gel column eluted successively with
petroleum ether-acetone gradient (100∶0 to 0∶100) to ob-
tain 10 fractions. Fraction 7 was further subjected to a silica
gel column chromatography with petroleum ether- acetone
SONG Zhi-Qin, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 81−83
82 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 2010 年 3 月 第 8 卷 第 2 期

(10∶1) to afford 11 major subfractions, F7a-F7k. F7a and
F7j were further separated on Sephadex LH-20
(CHCl3-MeOH, 1∶1) and MCI gel (MeOH-H2O, 9∶1),
respectively, to give F7aa–F7ad and F7ja–F7je. F7ac (170 mg)
and F7jd (80 mg), which were further subjected silica gel H
column separations eluted with CHCl3-MeOH (60∶1 and
100∶1), respectively, and afforded compounds 1 (15 mg), 2
(34 mg), and 3 (50 mg).
3 Results and discussion
Compound 1 was obtained as colorless colloid with
[α]19.3 D + 63.3 (c 0.15, CHCl3). Its molecular formula of
C45H55NO15 was determined by HR-ESI-MS (m/z 850.367 0,
[M + H]+). The IR spectrum of 1 showed the absorption
bonds for hydroxyl (3 436 cm–1), ester (1 745 cm–1) groups,
and aromatic ring (1 643, 1 592 and 709 cm–1). The NMR
data of 1 (Table 1) showed the presence of one benzoyl [δH
8.07 (2H, d, J = 7.4 Hz), 7.55 (1H, t, J = 7.4 Hz), 7.45 (2H, t,
J = 7.4 Hz); δC 164.8 (CO), 133.1, 130.1, 129.6, 128.4], one
nicotinyl [δH 9.29 (1H, d, J = 1.2 Hz), 8.83 (1H, br dd, J =2.0,
5.2 Hz), 8.37 (1H, br d, J = 8.4 Hz), 7.41 (1H, br s); δC 164.0
(CO), 153.8 (C), 151.5, 137.5, 125.2, 123.3], one isobuthyryl
[δH 2.88(1H, m), 0.93 (3H, d, J = 7.2 Hz), 0.62 (3H, d, J = 6.8
Hz); δC 174.8 (CO), 33.5 (CH), 18.8, 17.7 (CH3)], four acetyl
[δH 2.26, 2.12, 2.05, 2.00 (each CH3, s); δC 170.9, 170.5,
169.8, 168.1 (CO), 22.5, 20.9, 20.6, 20.5 (CH3)], and one
hydroxyl groups [δH 3.65 (1H, s)]. The remaining NMR sig-
nals consisted of 20 carbons, including one disubstituted
double bond [δH 6.17 (1H, d, J = 16.0 Hz), 5.75 (1H, dd, J =
9.2, 15.6 Hz); δC 133.9 and 131.8], one exocyclic double
bond [δH 4.41 (1H, s), 4.83 (1H, s ); δC 109.6 and 143.9], six
oxymethines [δH 5.93 (1H, br d, J = 6.0 Hz), 5.83, 5.67, 5.39,
5.21, and 5.17 (each 1H, s); δC 80.3, 71.7, 66.9, 70.9, 82.0,
and 79.3], three tertiary methyls [δH 1.46, 1.00, and 1.52
(each CH3, s); δC 23.6, 27.0 and 23.1], one secondary methyl
[δH 1.19 (3H, d, J = 7.2 Hz), δC 23.5], two secondary methi-
nes [δH 3.68 (1H, brs) and 2.91 (1H, dq, J = 7.6, 8.8 Hz); δC
44.8 and 37.4], one sp3 methene [δH 2.17 (1H, br s) and 2.83
(1H, d, J = 14.4 Hz); δC 50.1], and three sp3 quaternary car
bons (δC 41.1, 84.2 and 88.4). The afore-mentioned data
of 1 clearly indicated that it was a jatrophane diterpenoid
with one benzoyl, one nicotinyl, one isobutyryl, and four
acetyl groups, similar to those in the known diterpenoid,
pepluanin A [1].
Comparison of the NMR data of 1 with those of peplua-
nin A showed close similarities. In fact, the only difference
between 1 and pepluanin A is that the acetyl group. In
pepluanin A it was replaced by an isobutyryl group, implying
they likely shared the same basic structure except for one
different oxygenated group. The isobutyryl group was as-
signed to C-7 at δC 66.9 on the basis of HMBC correlations
of H-7 at δH 5.67 and two methyl signals of isobutyryl at δH
0.93 and 0.62 with the carbonyl (δC 174.8) of the isobutyrate.
The structure of 1 was finally established by careful analysis
of its 2D NMR spectra (1H-1H COSY, HMQC, and HMBC
data) as shown in Fig. 1.

Table 1 1H NMR (400 MHz) and 13C NMR (100 MHz) data of coumpound 1 in CDCl3 ( J in Hz)
No. δH δC No. δH δC
1α
1β
2.17 (br s)
2.83 (d, 14.4) 50.1 OAc — 168.1
2 — 88.4 2.26 (s) 22.5
3 5.93 (br d, 6.0) 80.3 2.12 (s) 20.9
4 3.68 (br s) 44.8 2.05 (s) 20.6
5 5.83 (s) 71.7 2.00 (s) 20.5
6 — 143.9 7-OiBu — 174.8
7 5.67 (s) 66.9 2.88(m) 33.5
8 5.39 (s) 70.9 0.93 (d, 7.2) 18.8
9 5.21 (s) 82.0 0.62 (d, 6.8) 17.7
10 — 41.1 3-OBz
11 6.17 (d, 16.0) 133.9 1 — 164.8
12 5.75 (dd, 9.2, 15.6) 131.8 — 130.1
13 2.91 (dq, 7.6, 8.8) 37.4 2, 6 8.07 (d, 7.4) 129.6
14 5.17 (s) 79.3 3, 5 7.45 (t, 7.4) 128.4
15 — 84.2 4 7.55 (t, 7.4) 133.1
16 1.46 (s) 23.6 9-ONiC — 164.0
17 4.41 (s) 4.83 (s) 109.6 8.83 (br dd, 2.0, 5.2) 153.8
18 1.00 (s) 27.0 9.29 (d, 1.2) 151.5
19 1.52 (s) 23.1 8.37 (br d, 8.4) 137.5
20 1.19 (d, 7.2) 23.5 — 125.2
OAc — 170.9 7.41 (br s) 123.3
— 170.5 15-OH 3.65 (s) —
— 169.8

SONG Zhi-Qin, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 81−83
2010 年 3 月 第 8 卷 第 2 期 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 83




Fig. 1 Structure and Key 1H-1H COSY (bold) and HMBC
correlations for compound 1

The relative configuration of 1 was deduced by analy-
zing the NOESY spectrum (Fig. 2), with reference to the data
reported for a large number of jatrophane diterpenoids al-
ready isolated. NOESY correlations of 15-OH with H-1β,
H3-16, and the ortho-benzoyl protons and of H-4 with H-3
defined the relative configuration of ring A, which exhibits a
trans ring junction. This feature has already been found for
all Δ6(17), Δ11-jatrophanes isolated from Euphorbia species
[1]. Among the NOE effects, the correlations of H3-19/H-8,
H3-18/H-11, H3-18/H-7, H3-20/H2-17, H-4/H-13, H-13/H11,
H-13/H-1α, H-11/H-7, H-5/H-8, and H-9/H-5 indicated the
relative stereochemistry of 1 as shown in Fig. 3, which is in
accordance with those of diterpenoids isolated earlier from E.
peplus [1-6]. Therefore, the structure of 1 was elucidated as 2α,
5α, 8α, 14β-tetraacetoxy-3β-benzoyloxy-7β-isobutyroyloxy-
9α-nico-inoyloxy-15β-hydroxyjatropha-6(17), 11E-diene,
named euphopeplin A (1).
The two known compounds were determined to be 2α,
5α, 7β, 8α, 9α, 14β-hexaacetoxy-3β-benzoyloxy-15-hy-
droxyjatropha-6(17), 11E-diene (2) and 5α, 8α, 9β, 10β,
14α-pentaacetoxy-3β-benzoyloxy-15-hydroxypepluane (3) by
comparison of their spectroscopic data with those reported in
the literature [4].



Fig. 2 Key NOESY correlations for compound 1

Euphopeplin A (1): Amorphous colloid; [α]19 D + 63.33 (c
0.15, CHCl3); IR (KBr) cm-1: 3 459, 2 977, 2 930, 2 855,
1 745, 1 643, 1 592, 1 365 and 709; ESI-MS m/z 850.4 [M +
H]+; (+)-HR-ESI-MS m/z 850.367 0 [M + H]+ (C45H56O15N+,
calcd. 850.364 9); 1H NMR (CDCl3, 400 Hz) and 13C NMR
(CDCl3, 100Hz) see Table 1.
The cytotixicity of compounds 1-3 was examined against
tumor cells (HL60, A549, and SW480). and the results
showed that all the tested compounds were inactive.
References
[1] Gabriella C, Ernesto F, Virginia L, et al. Jatrophane diter-
penes as modulators resistance. Advances of structure- activ-
ity relationships and discovery of the potent lead pepluanin A
[J]. J Med Chem, 2004, 47(4): 988-992.
[2] Amir RJ. Chemistry and biological activity of secondary
metabolites in Euphorbia from Iran [J]. Phytochemistry,
2006, 67(18): 1977-1984.
[3] Singla AK, Kamala P. Phytoconstituents of Euphorbia spe-
cies [J]. Fitoterapia, 1990, 61: 483-516.
[4] Jakupovic J, Morgenstern T, Bittner M, et al. Diterpenes
from Euphorbia peplus [J]. Phytochemistry, 1998, 47(8):
1601-1609.
[5] Hohmann J, Vasas A, Günther G, et al. Jatrophane diter- pe-
noids from Euphorbia peplus [J]. Phytochemistry, 1999,
51(5): 673-677.
[6] Seip EH, Hecker E. Derivatives of characiol, macrocyclic
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南欧大戟中一个新的假白榄烷型二萜
宋智琴 1, 2, 穆淑珍 1, 邸迎彤 3, 郝小江 1, 3*
1贵州省、中国科学院天然产物化学重点实验室, 贵阳 550002
2贵阳中医学院, 贵阳 550002
3中国科学院昆明植物研究所植物化学与西部植物资源国家重点实验室, 昆明 650204
【摘 要】 目的：研究南欧大戟全草的化学成分。方法：采用硅胶柱色谱、凝胶柱色谱和 MCI 等分离纯化化合物, 利用
ESI-MS, IR, NMR 确定化合物的结构。结果：分离鉴定了 3 个化合物, 分别为：euphopeplin A (1), 2α, 5α, 7β, 8α, 9α, 14β-hexa-
acetoxy-3β-benzoyloxy-15-hydroxyjatropha-6 (17), 11E-diene (2) 和 5α, 8α, 9β, 10β, 14α-pentaacetoxy-3β-benzoyloxy-15-hydroxy-
pepluane (3)。结论：化合物 1 为一新化合物。
【关键词】 大戟科; 大戟属; 南欧大戟; 二萜; 假白榄烷型二萜

【基金项目】贵州省优秀科技教育人才省长专项资金项目(No. 2008114); 贵州省中药现代化专项基金(No. 20065041);