全 文 ： 2010 年 3 月 第 8 卷 第 2 期 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 101








Diterpenes and Triterpenes from the Roots of
Euphorbia fischeriana

WU Qi-Cheng1, TANG Yu-Ping1*, DING An-Wei1, YOU Fen-Qiang2, DUAN Jin-Ao1
1Jiangsu Key Laboratory for TCM Formulae Research, Nanjing University of Chinese Medicine, Nanjing 210046;
2Affiliated Hospital, Nanjing University of Chinese Medicine, Kunshan 215300, China
[ABSTRACT] AIM: To study the terpenes in the roots of Euphorbia fischeriana. METHODS: The compounds were
isolated by silica gel column chromatography, and their structures were identified on the basis of physiochemical and
spectral data. RESULTS: Eight diterpenes and four triterpenes were obtained from the ethyl acetate extract, and their
structures were elucidated as jolkinolide A (1), jolkinolide B (2), prostratin (3), ent-kaurane-3-oxo-16α, 17-diol (4), an-
tiquorin (5), neriifolene (6), ent-atisane-3β, 16α, 17-triol (7), kauranoic acid (8), aleuritolic acid (9), 24-methyl- enecy-
cloartanol (10) and lupenyl acetate (11). CONCLUSION: Compounds 4-10 were isolated from this plant for the first
time.
[KEY WORDS] Euphorbia fischeriana; Lang-Du; Diterpene; Triterpene
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2010)02-0101-03
doi: 10.3724/SP. J. 1009.2010.00101
The roots of Euphorbia fischeriana, which is one of
the traditional Chinese medicines named “Lang-Du”, have
been used for the treatment of cancer, edema, and ascites[1].
Terpenes, especially diterpenes were thought to be the main
bioactive compounds in this plant with significant antitu-
mor activity against several tumor lines such as human
prostate LNCaP, sarcoma 180, Ehrlich ascites carci-
noma and hepatocellar carcinoma in mice[2-3]. In a further
chemical investigation of this plant, eight diterpenes, inclu-
ding jolkinolide A (1), jolkinolide B (2), prostratin (3), ent-
kaurane-3-oxo-16α, 17-diol (4), antiquorin (5), neriifolene
(6), ent-atisane-3β, 16α, 17-triol (7) and kauranoic acid (8),
and three triterpenes, including aleuritolic acid (9), 24-
methylenecycloartanol (10) and lupenyl acetate (11) were
isolated, their structures were identified on the basis of
physiochemical and spectral data. Compounds 4-10 were
isolated from this plant for the first time.
1 Apparatus and Reagents
Melting points were determined on a WRS-1B digital
melting point apparatus and were uncorrected. NMR spec-
tra were recorded on a Bruker Avance AV-500/300 NMR

[Received on] 00-000-2009
[Foundation Item] This project was supported by the National
Natural Science Foundation of China (No. 30672678) and 2009’
Program for New Century Excellent Talents by the Ministry of
Education.
[*Corresponding author] TANG Yu-Ping: Prof., Tel/Fax: 86-25-
85811916, E-mail: yupingtang@njutcm.edu.cn
spectrometer (Bruker; Rheinstetten, Germany) with TMS as
internal standard. MS spectra were obtained with a Q-TOF
Synapt mass spectrometer. Column chromatography was
carried out on silica gel (200-300 mesh, Qingdao Marine
Chemical Co., Ltd). All other chemicals were of analytical
grade.
2 Plant Material
The roots of Euphorbia fischeriana were collected in
Qiqihaer, Heilongjiang Province, China. The plant material
was identified by Prof. GUO Li-Na, Qiqihaer Medical Uni-
versity, China. A voucher specimen (No. NJUTCM-
20081028) was deposited in the Herbarium of Nanjing
University of Chinese Medicine, China.
3 Extraction and Isolation
Air-dried roots of E. fischeriana (14.0 kg) were ex-
tracted by 95% ethanol four times (3 d each) at room tem-
perature. The extracts were condensed in vacuo to afford
crude residue (3 200 g) which was suspended in H2O. The
aqueous suspension was subsequently partitioned succes-
sively with EtOAc to afford EtOAc fraction (910 g). A por-
tion of the EtOAc fraction (800 g) was subjected to column
chromatography on silica gel using a step gradient elution
of petroleum ether-EtOAc to yield compounds 1 (20 mg), 2
(130 mg), 3 (215 mg), 4 (176 mg), 5 (120 mg), 6 (25 mg), 7
(30 mg) 8 (23 mg), 9 (54 mg), 10 (98 mg) and 11 (980 mg).
4 Structure Identification
Compound 4 White amorphous powder (petroleum
WU Qi-Cheng, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 101−103
102 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 2010 年 3 月 第 8 卷 第 2 期

ether-EtOAc), mp174-175 °C; ESI-MS m/z 321 [M + H]+;
1H NMR (CDCl3, 300 MHz) δ: 3.42 (d, 1H, J = 15.0 Hz,
H-17), 3.39 (d, 1H, J = 15.0 Hz, H-17′), 2.49 (1H, d, J = 6.9
Hz, H-2), 2.47 (1H, d, J = 9.5 Hz, H-2′), 1.08 (3H, s, H-18),
1.07 (3H, s, H-20), 1.02 (3H, s, H-19); 13C NMR (CDCl3,
75 MHz) δ: 218.05(C, C-3), 79.64 (C, C-16), 69.84 (CH2,
C-17), 55.66 (CH, C-5), 54.38 (CH, C-9), 52.25 (CH2,
C-15), 47.13 (C, C-4), 43.31 (C, C-8), 40.86 (CH2, C-14),
40.68 (CH, C-13), 39.29 (CH, C-7), 38.54 (C, C-10), 37.87
(CH2, C-1), 34.03 (CH2, C-2), 27.31 (CH3, C-18), 26.58
(CH2, C-12), 21.21 (CH2, C-6), 20.94 (CH3, C-19), 19.28
(CH2, C-11), 17.60 (CH3, C-20). It was characterized as
ent-kaurane-3-oxo-16α, 17-diol by comparison of the
physical and spectral data with the literature[7].
Compound 5 Colorless needle crystal (petroleum
ether-EtOAc), mp 162-163 °C; ESI-MS m/z 317 [M + H]+;
The 1H NMR spectrum signals were exhibited for three
tertiary methyl groups at δ 1.08, 1.00, 0.85 (each 3H, s), an
exocyclic methylene group at δ 5.01 (lH, br s, H-17), 4.86
(lH, br s, H-17′) and a proton on the methine carbon atom
bearing an oxygen atom at δ 3.88 (d, lH, J = 3.0 Hz, H-13);
13C NMR (CDCl3, 75 MHz) δ: 217.89 (C, C-14), 215.88 (C,
C-3), 142.26 (C, C-16), 111.02 (CH2, C-17), 75.11 (CH,
C-13), 55.15 (CH, C-5), 51.11 (CH, C-9), 47.44 (C, C-8),
47.29 (C, C-4), 44.83 (CH, C-12), 43.69 (CH2, C-15), 37.54
(C, C-10), 36.69 (CH2, C-1), 34.01 (CH2, C-2), 30.39 (CH2,
C-7), 26.17 (CH3, C-18), 25.36 (CH2, C-11), 21.81 (CH3,
C-19), 19.94 (CH2, C-6), 13.66 (CH3, C-20). It was charac-
terized as antiquorin by comparison of the physical and
spectral data with the literature[8].
Compound 6 White needle crystal (petroleum
ether-EtOAc), mp 219-220 °C; ESI-MS m/z 319 [M + H]+;
The 1H NMR spectrum signals were exhibited for three
tertiary methyl groups at δ l.00, 0.76, 0.67 (each 3H, s), an
exocyclic methylene group at 4.99 (lH, br s, H-17), 4.84 (lH,
br s, H-17′) and two protons on methane carbon atoms
bearing an oxygen atom at 3.85 (lH, d, J = 2.4 Hz, H-13),
3.20 (lH, m, H-3); 13C NMR (CDCl3, 75 MHz) δ: 218.23 (C,
C-14), 142.74 (C, C-16), 110.75 (CH2, C-17), 78.89 (CH,
C-3), 75.14 (CH, C-13), 54.66 (CH, C-5), 52.01 (CH, C-9),
47.43 (C, C-8), 44.91 (CH, C-12), 43.97 (CH2, C-15), 38.69
(C, C-4), 37.84 (C, C-10), 36.43 (CH2, C-1), 30.81 (CH2,
C-7), 28.42 (CH2, C-2), 26.91 (CH2, C-11), 25.30 (CH3,
C-18), 18.83 (CH2, C-6), 15.57 (CH3, C-19), 14.06 (CH3,
C-20). It was characterized as neriifolene by comparison of
the physical and spectral data with the literature[8].
Compound 7 White amorphous powder (petroleum
ether-EtOAc); 1H NMR (C5D5N, 300 MHz) δ: 3.83, 3.94
(2H, Abq, J = 10.8 Hz, H-17), 3.44 (1H, dd, J = 5.1, 12.0
Hz, H-3), 1.22, 1.05, 0.99 (each 3H, s, 3 × Me); 13C NMR
(C5D5N, 75 MHz) δ: 78.38 (CH, C-3), 73.82 (C, C-16),
69.49 (CH2, C-17), 55.86 (CH, C-5), 53.69 (CH2, C-15),
52.24 (CH, C-9), 40.21 (CH2, C-7), 39.39 (C, C-4), 38.10
(CH2, C-1), 37.80 (C, C-8), 33.19 (C, C-10), 32.95 (CH,
C-12), 28.73 (CH3, C-18), 28.06 (CH2, C-2), 27.85 (CH2,
C-14), 23.96 (CH2, C-11), 23.76 (CH2, C-13), 19.04 (CH2,
C-6), 16.43 (CH3, C-19), 14.35 (CH3, C-20). It was charac-
terized as ent-atisane-3β, 16α, 17-triol by comparison of the
physical and spectral data with the literature[9].
Compound 8 White amorphous powder (petroleum
ether-EtOAc), mp 205-206 °C; 1H NMR (CDCl3, 300 MHz)
δ: 11.0 (1H, br s, COOH), 2.97 (1H, ddd, J = 6.0, 6.0, 12.0
Hz, H-16), 2.61 (1H, m, H-13), 2.47 (2H, m, H-2), 1.08 (3H,
s, H-18), 1.05 (3H, s, H-20), 1.03 (3H, s, H-19). These data
were consistent with those reported[10], therefore the com-
pound was characterized as kauranoic acid.
Compound 9 Colorless needle crystal (petroleum
ether-EtOAc). 1H NMR (CDCl3, 500 MHz) δ: 11.30 (1H,
br s, -COOH), 5.52 (1H, dd, J = 3.4, 7.7 Hz, H-15), 4.46
(1H, m, H-3), 2.37 (1H, m, H-16), 2.27 (1H, dd, J = 3.2,
14.4 Hz, H-16′), 2.04 (3H, s, CH3CO-), 0.95 (6H, s, 2 ×
Me), 0.94 (3H, s), 0.92 (6H, s, 2 × Me), 0.88 (3H, s, H-24),
0.85 (3H, s, H-23); 13C NMR (CDCl3, 75 MHz) δ: 185.73
(C-28), 172.85 (CH3CO-), 162.50 (C-14), 118.74 (C-15),
82.82 (C-3), 57.55 (C-5), 53.35 (C-17), 51.02 (C-9), 43.40
(C-18), 42.73 (C-7), 40.97 (C-8), 39.87 (C-10), 39.60 (C-4),
39.34 (C-1), 39.26 (C-13), 37.30 (C-19), 35.62 (C-21),
35.26 (C-12), 33.81 (C-29), 33.28(C-16), 32.67(C-22),
31.21 (C-20), 30.56 (C-30), 29.87 (C-23), 28.07 (C-26),
25.39 (C-2), 24.36 (C-27), 23.16 (CH3CO-), 20.65 (C-6),
19.23 (C-11), 18.50 (C-24), 17.53 (C-25). It was chara-
cterized as acetyl aleuritolic acid by comparison of the
physical and spectral data with the literature[11].
Compound 10 White lamellar crystal (MeOH); 1H
NMR (CDCl3, 500 MHz) δ: 4.72 (1H, s, H-31), 4.66 (1H, s,
H-31′), 3.29 (1H, m, H-3), 1.02 (3H, d, J = 3.0 Hz, H-27),
1.01 (3H, d, J = 3.0 Hz, H-26), 0.97 (6H, s, H-18, H-29),
0.90 (3H, s, H-28), 0.89 (3H, d, J = 5.0 Hz, H-21), 0.81 (3H,
s, H-30), 0.56 (1H, d, J = 4.0 Hz, H-19a), 0.33 (1H, d, J =
4.3 Hz, H-19b); 13C NMR (CDCl3, 125 MHz) δ: 157.04 (C,
C-24), 105.96 (CH2, C-31), 78.82 (CH, C-3), 52.21 (CH,
C-17), 48.95 (C, C-14), 48.01 (CH, C-8), 47.14 (CH, C-5),
45.47 (C, C-13), 40.5 (C, C-4), 36.05 (CH, C-20), 35.68
(CH2, C-12), 34.97 (CH2, C-22), 33.77 (CH, C-25), 32.89
(CH2, C-15), 32.02 (CH2, C-1), 31.3 (CH2, C-23), 30.37
(CH2, C-2), 29.81 (CH2, C-19), 28.23 (CH2, C-7), 26.49
(CH2, C-16), 26.26 (C, C-10), 25.93 (CH2, C-11), 25.34
(CH3, C-30), 21.87 (CH3, C-27), 21.74 (CH3, C-26), 21.23
(CH2, C-6), 20.04 (C, C-9), 19.11 (CH3, C-28), 18.36 (CH3,
C-21), 17.95 (CH3, C-18), 14.01 (CH3, C-29). It was char-
acterized as 24-methylenecycloartanol by comparison of the
physical and spectral data with the literature [12].
Compounds 1, 2, 3 and 11 isolated from this plant
were identified as jolkinolide A, jolkinolide B , prostratin and
lupenyl acetate .by comparison of the spectral data with
those reported in literature[4-6, 13].
WU Qi-Cheng, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 101−103
2010 年 3 月 第 8 卷 第 2 期 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 103

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狼毒大戟中二萜和三萜类成分
吴起成 1, 唐于平 1*, 丁安伟 1, 尤奋强 2, 段金廒 1
1 南京中医药大学 江苏省方剂研究重点实验室, 南京 210046
2 南京中医药大学昆山附属医院, 昆山 215300
【摘 要】 目的：对狼毒大戟的萜类成分进行研究。方法: 采用硅胶柱层析色谱技术分离并纯化化合物, 根据理化性
质及波谱技术鉴定其结构。结果: 从狼毒大戟的乙酸乙酯部位中分离得到 8 个二萜化合物和 3 个三萜化合物, 分别鉴定为
岩大戟内酯 A (1), 岩大戟内酯 B (2), prostratin (3), ent-kaurane-3-oxo-16α, 17-diol (4), antiquorin (5), neriifolene (6), ent- ati-
sane-3β, 16α, 17-triol (7), kauranoic acid (8), 乙酰木油树酸 (9), 24-亚甲基环木菠萝烷醇 (10), 乙酰羽扇豆醇 (11)。结论: 化
合物 4-10 为首次从该植物中分得。
【关键词】 狼毒大戟; 狼毒; 二萜; 三萜

【基金项目】 国家自然科学基金资助项目(No. 30672678); 国家教育部新世纪优秀人才支持计划(2009 年度)