全 文 ：264 Chin J Nat Med July 2010 Vol. 8 No. 4 2010 年 7 月 第 8 卷 第 4 期








Chemical Constituents from the Roots of Vernicia fordii
XIE Yu-Feng1, TAO Zheng-Ming3, WANG Hong-Bing2, QIN Guo-Wei2*
1Guang-Dong College of Pharmacy, Guangzhou 510006;
2Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203;
3Zhejiang Institute of the Subtropical Crops, Wenzhou 325005, China
[ABSTRACT] AIM: To study the chemical constituents of the roots of Vernicia fordii (Hemsl.) Airy Shaw (Euphor-
biaceae). METHODS: Compounds were isolated by repeatedly column chromatography over silica gel and Sephadex
LH-20. Their structures were identified by spectral analysis and comparison with the literature. RESULTS: Six com-
pounds were isolated and identified as 12-O-palmityl-13-O-acetyl-16-hydroxyphorbal (1), aleuritin (2), (-) syringaresi-
nol (3), daucosterol (4), 4-hydroxy-3, 5-dimethoxybenzolic acid (5) and acetyl aleuritolic acid (6). CONCLUSION:
Compounds 3-6 were reported from the plant for the first time.
[KEY WORDS] Vernicia fordii, Chemical constituents; Diterpenoid
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2010)04-0264-03
doi: 10.3724/SP. J. 1009.2010.00264
1 Introduction
Vernicia fordii (Hemsl.) Airy Shaw (syn. Aleurites
fordii, Euphorbiaceae) is a perennial deciduous tree. A com-
mercially important product “tung oil” is produced from the
seeds of this plant. The seeds, leaves and roots of the plant
are used medicinally for anti-inflammation purposes [1].
Chemical investigation of the plant revealed 12-O-palmityl-
13-O-acetyl-16-hydroxyphorbol and 13-O-acetyl-16-hydro-
xyphorbol from the fruit, aleuritin, a coumarinolignoid from
the stems, and several flavonoids and triterpenoids from the
leaves and roots [2-4]. In order to search for the bioactive
principles from Euphorbiaceae plants, we re-investigated
the chemical constituents of the plant roots. In the course of
our study six compounds were isolated and identified as
12-O-palmityl-13-O-acetyl-16-hydroxyphorbol (1), aleuri-
tin (2), (-) syringaresinol (3), daucosterol (4), 4-hydroxy-3,
5-dimethoxy-benzolic acid (5) and acetyl aleuritolic acid
(6). Compounds 3-6 were reported from the plant for the
first time.
2 Experimental
2.1 General
The IR spectrum was recorded on Perkin Elmer 577
spectrophotometer. The specific rotation was obtained with
Perkin Elmer 241 MC polarimeter. The NMR spectra were

[Received on] 07-Apr-2010
[Research Funding] This project was supported by Young Re-
search Grant from Chinese Academy of Sciences (No.
SIMM0709QN-05)
[*Corresponding author] QIN Guo-Wei: Prof., Tel: 86-21-
50805853, E-mail: gwqin@mail.shcnc.ac.cn
recorded on Bruker AM-400 with TMS as an internal stan-
dard. EI-MS and ESI-MS were carried out on MAT 95. and
Bruker esqure3000plus spectrometers. Silica gel (200-300
μm) used for column chromatography, and pre-coated silica
GF254 plates used for TLC were purchased from Qingdao
Marine Chemical Co., Ltd.). Sephadex LH-20 is from
Pharmacia
2.2 Plant material
The roots of Vernicia fordii were collected from
Wenzhou area in 2007, and identified by Prof. TAO
Zheng-Ming of Zhejiang Institute of Subtropical Crops,
where a voucher specimen is deposited.
2.3 Extraction and isolation
The dried roots of Vernicia fordii (4.4 kg) were pow-
dered and extracted with 95% ethanol. The extract was
evaporated under reduced pressure to give a residue which
was suspended in H2O and extracted successively with pe-
troleum ether, CHCl3, EtOAc and BuOH to obtain four frac-
tions. The fraction of CHCl3 (22 g) was subjected to re-
peated chromatography over silica gel and Sephadex LH-20
to yield compounds 1 (16 mg), 2 (24 mg), 3 (14 mg). 4 (16
mg), 5 (24 mg), and 6 (14 mg), respectively.
2.4 Identification
Compound 1 Colorless needles, mp: 176-178°C;
C38H60O9, MW 660, (+) ESI-MS m/z 683 [M + Na]+, (-)
ESI-MS m/z 705 [M + HCOO]―, 1H NMR (400 MHz,
CDCl3) δ: 0.88 (3H, t, J = 7.0, chain terminal CH3), 0.91
(3H, d, J = 6.4 Hz, 18-CH3), 1.29 (28H, br s, CH2 × 14 in
palmityl), 1.33 (3H, s, 17- CH3), 1.76 (3H, s, 19- CH3), 2.11
(3H, s, OAc), 2.41, 2.63 (each 1H, d, J = 19.4 Hz, 5-H2),
3.21 (1H, m, H-8 or H-10), 3.34 (1H, m, H-8 or H-10), 3.81
(2H, s, 16-H2), 4.00 (2H, s, 20-H2), 5.45 (1H, d, J = 10 Hz,
XIE Yu-Feng, et al. /Chinese Journal of Natural Medicines 2010, 8(4): 264−266
2010 年 7 月 第 8 卷 第 4 期 Chin J Nat Med July 2010 Vol. 8 No. 4 265

H-12), 5.67 (1H, s, H-7), 7.57 (1H, s, H-1); 13C NMR and
DEPT (100 MHz, CDCl3) δ: 10.00 (C-19), 14.09 (C-17),
14.50 (C-18), 18.79 (CH3, chain terminal), 20.99 (CH3CO),
22.66, 25.05, 28.99, 29.23, 29.32, 29.47, 29.56, 29.62,
29.65 (CH2 × n in chain), 31.66 (C-15), 31.89, 34.49 (CH2
× 2 in chain), 36.49 (C-14), 38.15 (C-5), 38.97 (C-8),
42.94 (C-11), 55.79 (C-10), 62.08 (C-16), 65.83 (C-13),
67.94 (C-20), 73.36 (C-4), 76.32 (C-12), 78.10 (C-9),
128.79 (C-7), 133.17 (C-2), 140.81 (C-6), 160.56 (C-1),
173.35, 173.69 (two ester carbonyls), 209.55 (C-3). Above
data were in accordance with 12-O-palmityl-13-O- ace-
tyl-16- hydroxyphorbol from fruits of the same plant. As-
signment of 1H NMR and 13C NMR data was made by
comparison with similar structures in the same solvent [6-7].
Compound 2 Amorphous powder; C21H20O9, MW 416,
(+) ESI-MS m/z 417 [M + 1]+, 855 [2M + Na]+, (−) ESI-MS
m/z 415 [M − 1]―, IR (KBr) νmax: 3 450, 1 737, 1 618,
1 524, 1 452, 1 113, 1 086, 1 030, 829 cm-1, 1H NMR (400
MHz, C5D5N) δ: 3.83 (3H, s, 7-OCH3), 3.84 (6H, s, 2’,
5’-OCH3), 3.95 (1H, dd, J = 3.2 Hz, 12.8 Hz, H-9’), 4.29
(1H, dd, J = 2.0, 12.8 Hz, H-9’b), 4.41 (1H, m, H-8’), 5.56
(1H, d, J = 8.0 Hz, H-7), 6.35 (1H, d, J = 9.8 Hz, H-3), 6.68
(1H, s, H-8), 7.23 (2H, s, H-2’, 6’), 8.00 (1H, d, J = 9.8 Hz,
H-4); 13C NMR and DEPT (100 MHz, C5D5N) δ: 56.21
(4-OCH3), 56.41 (3’, 5’-OCH3), 61.13 (C-9’), 78.19 (C-7’),
79.43 (C-8’), 93.02 (C-8), 103.61 (C-4a), 106.19 (C-2’, 6’),
111.93 (C-3), 126.66 (C-1’), 130.41 (C-6), 138.46 (C-4, 4’),
140.34 (C-5), 149.37 (C-3’, 5’), 149.55 (C-7), 152.88
(C-8a), 161.26 (C-2); HSQC (C5D5N) correlation: H-3/δ
111.93 (C-3), H-4/δ 138.46 (C-4), 7-OCH3/152.88 (C-8a),
H-8/δ 93.02 (C-8), H-2’, 6’/δ 106.19 (C-2’, 6’), H-7’/δ
78.19 (C-7’), H-8’/δ 79.43 (C-8’), H-9’/δ 61.13 (C-9’); 3’,
5’-OCH3/δ 56.41, 4-OCH3/δ 56.21; HMBC (C5D5N) corre-
lation: H-3/δ 103.61 (C-4a), 152.88 (C-8a), H-4/δ 140.34
(C-5), 149.55 (C-7), 152.88 (C-8a), H-8/δ 103.61 (C-4a),
130.41 (C-6), 149.55 (C-7), 152.88 (C-8a), 3’,5’-OCH3/δ
106.19 (C-2’, 6’), H-2’,6’/δ 138.46 (C-4’), 149.37 (C-3’,
5’), H-7’/δ 61.13 (C-9’), 79.43 (C-8’), 106.19 (C-2’, 6’),
126.66 (C-1’), H-8’/δ 78.19 (C-7’), H-9’/δ 78.19 (C-7’),
ROESY (C5D5N) correlation: H-3/H-4, H-8/7-OCH3, H-2’
6’/3’ 5’-OCH3, H-7’, H-8’, 3’ 5’-OCH3/H-2’ 6’, H-9;
Above data were in accordance with aleuritin from stems of
same plant[3]. Assignment of 1H NMR and 13C NMR data
was made by 2D NMR techniques.
Compound 3 Colorless needles, mp: 181-182°C;
C22H26O8, MW 418, (+) ESI-MS m/z 441[M + Na]+, 859
[2M + Na]+, (−) ESI-MS m/z: 417 [M − 1]―, 857 [2M + Na
− 2H]―; [α]D= −8.2° (c 0.5, CHCl3), 1H NMR (400 MHz,
CDCl3) δ: 3.07 (2H, m, H-8, 8’), 3.86 (12H, s, 4 × OCH3),
3.88 (2H, dd, J = 4.0, 9.0 Hz, Ha-9, 9’), 4.26 (2H, dd, J =
6.8, 9.0 Hz, Hb-9, 9’), 4.71 (2H, d, J = 4.4 Hz, H-7, 7’),
5.61 (2H, s, 2 × OH), 6.56 (4H, s, H-2, 2’, 6, 6’); 13C NMR
and DEPT (100 MHz, CDCl3) δ: 54.17 (C-8, 8’), 56.21 (4
× OCH3), 71.65 (C-9, 9’), 85.92 (C-7, 7’), 102.55 (C-2, 2’,
6, 6’), 131.90 (C-1, 1’), 134.14 (C-4, 4’), 147.04 (C-3, 3’, 5,
5’). Above data were identical with those of (-) syringa-
resinol [8].
Compound 4 Amorphous powders; C35H60O7, MW
576, (+) ESI-MS m/z 599 [M + Na]+, (−) ESI-MS m/z: 621
[M + HCOO]−, IR (KBr) νmax: 3 421, 1 635, 1 463, 1 378,
1 076, 1 024, 599 cm−1; 1H NMR (400 MHz, C5D5N) δ:
0.66 (3H, s, 18-CH3), 0.85-0.89 (9H, 21, 26, 27-CH3), 0.93
(3H, s, 19-CH3), 0.98 (3H, d, J = 6.8 Hz, 19-CH3), 3.98 (2H,
m, glu-2’, 5’), 4.01 (1H, m, H-3), 4.32 (2H, m, glu-3’, 4’),
4.45 (1H, dd, J = 5.2, 11.4 Hz, glu-6a), 4.60 (1H, dd, J =
2.0, 11.4 Hz, glu-6b), 5.08 (1H, d, J = 8.0 Hz, glu-1), 5.35
(1H, d, J = 4.8, H-6); 13C NMR and DEPT (100 MHz,
C5D5N) δ: 11.96 (C-18), 12.14 (C-29), 18.99 (C-26), 19.18
(C-21), 19.41 (C-19), 19.98 (C-27), 21.26 (C-11), 23.35
(C-28), 24.50 (C-15), 26.29 (C-23), 28.54 (C-16), 29.60
(C-25), 30.24 (C-2), 32.02 (C-8), 32.16 (C-7), 34.16 (C-22),
36.38 (C-20), 36.90 (C-10), 37.45 (C-1), 39.31 (C-4), 39.91
(C-12), 42.45 (C-13), 45.99 (C-24), 50.30 (C-9), 56.19
(C-17), 56.79 (C-14), 62.79 (C-6’), 71.64 (C-4’), 75.36
(C-2’), 78.01 (C-3’), 78.55 (C-3), 78.62(C-5’), 102.55
(C-1’), 121.94 (C-6), 140.86 (C-5). Above data were iden-
tical with those of daucosterol [9].
Compound 5 Amorphous powder; C9H10O5, MW
198, EI-MS m/z 198 [M]+, 183 [M − CH3]+, 1H NMR (400
MHz, CDOD3) δ: 3.87 (6H, s, 2 × OCH3), 7.32 (2H, s, H-2,
6). The data were identical with 4-hydroxy-3, 5-dimethoxy-
benzolic acid [10].


Compound 6 Amorphous powders; C32H50O4, MW
498, (+) ESI-MS m/z: 521 [M + Na]+, 1019 [2M + Na]+, (−)
ESI-MS m/z: 497 [M − H]―, 1 018 [2M + Na − H]―; 1H
NMR (400 MHz, CDCl3) δ: 0.84, 0.88, 0.91, 0.92, 0.93,
0.95, 0.95 (each 3H, s, 7 × CH3), 2.04 (3H, s, CH3CO),
2.27 (1H, dd, J = 2.8, 14.0 Hz, H-16β) 2.37 (1H, dd, 8.0,
14.0 Hz, H-16α), 4.46 (1H, dd, J = 6.0, 9.2 Hz, H-3), 5.52
(1H, dd, J = 3.4, 7.8 Hz, H-15); 13C NMR and DEPT (100
MHz, CDCl3) δ:15.62 (C-25), 16.58 (C-24), 17.29 (C-11),
18.71 (C-6), 21.29 (CH3CO), 22.44 (C-27), 23.44 (C-2),
26.17 (C-26), 27.94 (C-23), 28.64 (C-30), 29.29 (C-20),
29.69 (C-22), 30.68 (C-16), 31.85 (C-29), 33.30 (C-12),
33.64 (C-21), 35.31 (C-19), 37.24 (C-13), 37.36 (C-1),
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266 Chin J Nat Med July 2010 Vol. 8 No. 4 2010 年 7 月 第 8 卷 第 4 期

37.66 (C-4), 37.91 (C-10), 39.01 (C-8), 40.73 (C-7), 41.38
(C-18), 49.04 (C-9), 51.45 (C-17), 55.56 (C-5), 80.87 (C-3),
116.81 (C-15), 160.54 (C-14), 170.01 (CH3CO), 183.90
(C-28); Above 1H NMR and 13C NMR data were identical
with those of acetyl aleuritolic acid [11].
3 Results and Discussion
Phorbol esters have been reported to exhibit a wide
variety of biological activities, especially anti-tumor and
anti-HIV, which attracts worldwide interests for further
extensive study. Recently, a phorbol ester named “pros-
tratin” (i.e. 12-deoxy-phorbol-13-acetate) has been ap-
proved for clinical trial in the United States as anti-HIV
agent. Compound 1 is a known phorbol diester, isolated
first in 1975 from the fruit of Vernicia fordii [2]. At that time
its structure was determined by partial synthesis from
13-O-acetyl-16-hydroxyphorbol, a known monoester to-
gether with the analysis of 1H NMR data at 90 MHz. Dur-
ing our re-investigation compound 1 was isolated from
plant roots and its high resolution 1H NMR and 13C NMR
data were reported for the first time.
Coumarinolignoids are a relatively new and rare
group of natural products consisting of coumarin moieties
with the phenyl propanoid units through a 1, 4-dioxane
bridge. Aleuritin, a Coumarinolignoid was isolated from the
stems of Vernicia fordii in 1989 [2]. In the course of our
study compound 2 isolated from roots of the plant was
identified as aleuritin. Its 2D NMR data are reported here for
the first time.
Compounds 3-6 were identified by spectral analysis
and comparison with literature data. They are obtained from
the plant for the first time. Compound 6 is a commonly-
occurring oleanane-type triterpenoid, but with a rare double
bond between C14 and C15, which showed great difference
of chemical shifts in 13C NMR spectrum (δ 160.54 of C-14
and 116.81 of C-15 for 6). It is reported to have antibacte-
rial activity against Staphylococcus aurens and Salmonella
typhimurium in vitro tests [5].
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油桐根的化学成分
谢郁峰 1, 陶正明 3, 王红兵 2, 秦国伟 2*
1 广东药学院, 广州 510006; 2 中国科学院上海药物研究所, 上海 201203; 3 浙江省亚热带作物研究所, 温州 325005
【摘 要】 目的: 对大戟科植物油桐 (Vernicia fordii (Hemsl.) Airy Shaw) 根的化学成分进行研究。方法: 运用多种层
析方法进行分离纯化，通过波谱解析进行结构鉴定。结果：从油桐根的乙醇提取物中分离并鉴定出 6 种成分, 它们是
12-O-palmityl-13-O-acetyl-16-hydroxyphorbal (1), aleuritin (2), (-) syringaresinol (3), daucosterol (4), 4-hydroxy-3,
5-dimethoxybenzolic acid (5) 和 acetyl aleuritolic acid (6). 其中 1 和 2 首次从根中分得, 并补充了一些 NMR 研究。结论：
化合物 3-6 为本植物中首次报道, 6 是齐墩果烷型三萜, 结构中具有△14,15, 在天然界较少见。
【关键词】 油桐根；化学成分；二萜

【基金项目】中国科学院知识创新工程青年人才领域前沿项目(No. SIMM0709QN-05)