全 文 ： 2011 年 5 月 第 9 卷 第 3 期 Chin J Nat Med May 2011 Vol. 9 No. 3 185

Chinese Journal of Natural Medicines 2011, 9(3): 0185−0187
doi: 10.3724/SP.J.1009.2011.00185
Chinese
Journal of
Natural
Medicines







Chemical Constituents of Parabarium huaitingii
LEI Ting1, JIANG Hai-Yan2, HU Ying1, CEN Ying-Zhou1*
1Department of Chemistry, Jinan University, Guangzhou 510632, China;
2Guangdong Provincial Material Testing Center, Guangzhou 510632, China
Available online May 2011
[ABSTRACT] AIM: To investigate the chemical constituents of Parabarium huaitingii. METHODS: The constituents were isolated
and purified by silica gel column chromatography and preparative TLC. Their structures were identified on the basis of spectral data
and physiochemical properties. RESULTS: Nine compounds were isolated and their structures were elucidated as physcion (1), fu-
maric acid (2), methyl gentisate (3), 4-hydroxy-3, 5-dimethoxybenzoic acid methyl ester (4), syringic acid (5), 2, 5-dimethoxy-p-
benzoquinone (6), vanillic acid (7), 3, 4, 5-trimethoxybenzoic acid (8) and 6-methoxy-7-hydroxycoumarin (9). CONCLUSION: All of
the compounds were isolated from this genus for the first time.
[KEY WORDS] Parabarium huaitingii; Chemical constituents
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)03-0185-03

1 Introduction
Parabarium huaitingii (Apocynaceae) is widely distri-
buted in Guangxi and Guangdong provinces. As a well-
known folk medicine, it has been usually used to treat rheu-
matoid arthritis and bruises. Up to now, there was one re-
port about studies on the chemical constituents in the genus
Parabarium. In this report, three phenylpropanoid-substituted
epicatechin glycosides showing good antioxidative activity
[1]were obtained. During our investigations on constituents of
P. huaitingii, nine compounds were isolated and elucidated as
physcion (1), fumaric acid (2), methyl gentisate (3),
4-hydroxy-3, 5-dimethoxybenzoic acid methyl ester (4), sy-
ringic acid (5), 2, 5-dimethoxy-p-benzoquinone (6), vanillic
acid (7), 3, 4, 5-trimethoxybenzoic acid (8) and
6-methoxy-7-hydroxycoumarin (9). All of these compounds
were obtained from this genus for the first time.
2 Apparatus and Reagents
Melting points were determined on an X-6 mi-
cro-melting point apparatus and are uncorrected. FTIR spec-
tra were obtained on a Bruker Equinox-55 FTIR Spectrome-

[Received on] 02-Sep.-2010
[Research Funding] This project was supported by the National
Natural Science Foundation of China (No. 20772047).
[*Corresponding author] CEN Ying-Zhou: Prof., Tel: 86-20-
85223420, E-mail: ofx@jnu.edu.cn
These authors have no any conflict of interest to declare.
ter. NMR spectra were recorded on Varian Inova-500 with
TMS as reference. The EI-MS were measured on Bruker
Daltonics APEXⅡ4.70. Silica gel used for column chroma-
tography (CC) was supplied by Qingdao Marine Chemical
Factory, Qingdao, China.
3 Plant Material
The barks of P. huaitingii were purchased in Nanning
Guangxi province, China and identified by Prof. Jimmy
Zhenqiu. A voucher specimen was deposited in the Natural
Medicines Research, Department of Chemistry, Jinan Univer-
sity, China.
4 Extraction and Isolation
The barks of P. huaitingii (20 kg) were extracted three
times with 80% ethanol at room temperature. The solvent
was evaporated off under vacuum to yield 2.7 kg of crude
extract, which was suspended in H2O and partitioned with
petroleum ether, CHCl3, EtOAc and n-BuOH, respectively.
The petroleum ether extract (140 g) was subjected to silica
gel column (200-300 mesh) and eluted with petroleum
ether-EtOAc (100 : 0-0 : 100) to get Frs. 1-16. From Fr. 4,
compound 1 (2 mg) was obtained by repeated silica gel CC
with petroleum ether-EtOAc (9 : 1). The CHCl3 extract (90 g)
was subjected to column chromatography(CC) over silica gel
(200-300 mesh) and eluted with petroleum ether-acetone
(100 : 0-0 : 100) to get Frs. 1-10. From Fr. 2, compound 3 (21
mg) was obtained by silica gel CC and preparative TLC. Fr. 3
LEI Ting, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 185−187
186 Chin J Nat Med May 2011 Vol. 9 No. 3 2011 年 5 月 第 9 卷 第 3 期

was further purified by silica gel CC with petrol-CHCl3 to
yield compound 4 (45 mg). From Fr. 5, compounds 5 (13 mg),
7 (3 mg) and 8 (12 mg) were obtained by repeated silica gel
CC. Compound 6 (4 mg) was yielded from Fr. 7. The EtOAc
extract (300 g) was subjected to column chromatography (CC)
over silica gel (200-300 mesh) and eluted with CHCl3-MeOH
to get Frs. 1-10. From Fr. 1, compound 2 (42 mg) was ob-
tained by recrystallization. Compound 9 (7 mg) was obtained
by repeated silica gel CC from Fr. 2.
5 Identification
Compound 1 Red needle crystal (CHCl3), mp
207–209 °C; EI-MS m/z 284, 255, 241, 128. 1H NMR (400
MHz, CDCl3) δ：12.25 (1H, s, -OH), 12.05 (1H, s, -OH), 7.56
(1H, s, H-5), 7.31 (1H, d, J = 2.4 Hz, H-4), 7.02 (1H, s, H-7),
6.62 (1H, d, J = 2.4 Hz, H-2), 3.87 (3H, s, 3-OCH3), 2.38 (3H,
s, 6-CH3). These data were identical with those of physcion
[2].
Compound 2 Pale yellow block crystal (EtOAc-
EtOH), mp 300–302 °C; IR (KBr) υ: 3 443, 3 383, 3 085,
1 670, 1 584, 1 422, 1 277, 1 232, 1 067, 647 cm-1.
EI-MS m/z 116, 98, 88, 81, 72, 53. 1H NMR (400 MHz,
(CD3)2CO) δ: 7.65 (2H, dd, J = 14 Hz), 11.82 (2H, br,
-COOH). These data were identical with those of fumaric
acid [3].
Compound 3 Light yellow needle crystal (EtOAc), mp
85–87 °C; IR (KBr) υ: 3 337, 3 139, 2 960, 1 687, 1 618,
1 510, 1 437, 1 337, 1 215, 1 081, 976, 783, 686 cm-1.
EI-MS m/z 168, 136, 108, 80, 52. 1H NMR (400 MHz,
CDCl3) δ：7.30 (1H, d, J = 3.2 Hz), 7.03 (1H, dd, J = 3.2,
8.8 Hz), 6.89 (1H, d, J = 8.8 Hz), 3.95 (3H, s, -OCH3);
13C NMR (100 MHz, CDCl3) δ: 170.19, 155.68, 147.85,
124.15, 118.48, 114.83, 112.21, 52.36. These data were
identical with those of methyl gentisate [4].
Compound 4 Light yellow needle crystal (EtOAc), mp
105–107 °C; IR (KBr) υ: 3 369, 3 312, 1 701, 1 616,
1 516, 1 462, 1 431, 1 337, 1 238, 1 118, 993, 758 cm-1.
EI-MS m/z 212, 197, 181, 153, 141. 1H NMR (400 MHz,
CDCl3) δ：7.32 (2H, s, H-2, 6 ), 6.03 (1H, s, 4-OH), 3.92 (6H,
s, 3,5-OCH3), 3.89 (3H, s, -COOCH3); 13C NMR (100 MHz,
CDCl3) δ: 166.83 (>C=O), 146.67 (C-3, 5), 139.3 (C-4),
121.04 (C-1), 106.71 (C-2, 6), 56.39 (3, 5-OCH3),
52.03 (-OCH3). These data were identical with those of
4-hydroxy-3, 5-dimethoxybenzoic acid methyl ester [5].
Compound 5 Colorless needle crystal (EtOAc-EtOH),
mp 205–206 °C. IR (KBr) υ: 3 374, 1 698, 1 618, 1 562,
1 525, 1 456, 1 417, 1 368, 1 201, 1 116, 772, 692 cm-1.
EI-MS m/z 198 (100), 183 (32), 127 (17), 109 (11). 1H NMR
(400 MHz, CDCl3) δ: 7.40 (2H, s, H-2,6), 3.96 (6H, s, 3,
5-OCH3); 13C NMR(100 MHz, CDCl3) δ:170.68 (-COOH),
146.72(C-3,5), 140.06 (C-4), 119.98 (C-1), 107.33 (C-
2,6), 56.47 (3, 5-OCH3). These data were identical with
those of syringic acid [6].
Compound 6 Yellow needle crystal (EtOAc), mp 278–
280 °C. IR (KBr) υ: 3 443, 3 127, 1 627, 1 567, 1 479,
1 368, 1 320, 1 269, 1 221, 1 161, 996, 777 cm-1. EI-MS
m/z 168, 138, 125, 112, 97, 80, 69. 1H NMR (400 MHz,
CDCl3) δ: 5.86 (2H, s, H-3, 5), 3.82 (6 H, s, 2,6-OCH3).
These data were identical with those of 2,
5-dimethoxy-p-benzo- quinone [7].
Compound 7 White powder (EtOAc), mp 250–252
°C. IR (KBr) υ: 3 485, 3 096, 2 925, 2 849, 1 687, 1 599, 1
559, 1 525, 1 437, 1 280, 1 116, 1 070, 760, 513 cm-1.
EI-MS m/z 168, 153, 125, 97, 51. 1H NMR (400 MHz,
DMSO) δ: 12.47 (1H, br s), 9.82 (1H, br s), 7.44 (1H,
dd, J = 2.0, 7.6 Hz), 7.43 (1H,d, J = 2.0 Hz), 6.84 (1H,dd,
J = 2.0, 1.6 Hz), 3.81 (3H, s, -OCH3). These data were iden-
tical with those of vanillic acid [8].
Compound 8 White needle crystal (EtOAc), mp 166–
168 °C. IR (KBr) υ: 3 445, 3 122, 1 692, 1 590, 1 562,
1 510, 1 468, 1 411, 1 323, 1 272, 1 223, 1 124, 1 067,
993, 860, 763, 715 cm-1. EI-MS m/z 212, 197, 154, 141, 93.
1H NMR (400 MHz, CDCl3) δ: 7.83 (2H, s, H-2, 6), 3.94 (3H,
s, 4-OCH3), 3.93 (6H, s, 3, 5-OCH3); 13C NMR (100 MHz,
CDCl3) δ: 171.68 (> C=O), 152.98 (C-3, 5), 143.05 (C-4),
124.05 (C-1), 107.45 (C-2, 6), 60.95 (C-4), 56.25 (C-3, 5).
These data were identical with those of 3, 4,
5-trimethoxybenzoic acid [9].
Compound 9 Light yellow needle crystal (EtOAc), mp
204–206 °C. IR (KBr) υ: 3 451, 3 377, 2 917, 2 854,
1 709, 1 610, 1 564, 1 508, 1 437, 1 292, 1 263, 1 135,
1 067, 865, 593 cm-1. EI-MS m/z 192, 177, 149, 121, 69.
1H NMR (400 MHz, CDCl3) δ: 7.60 (1H, d, J = 7.6 Hz), 6.93
(1H, s), 6.85 (1H, s), 6.27 (1H, d, J = 7.6 Hz), 6.13 (1H, s,
-OH), 3.96 (3H, s, -OCH3). These data were identical with
those of 6-methoxy-7- hydroxycoumarin [10].
Acknowledgements
Authors are thankful to Prof. LIN Yong-Cheng (SUN
Yat-Sen University, China) for his help in the NMR spectra
measurement.
References
[1] Tang JS, Gao H, Wang CX, et al. Antioxidative phenylpro-
panoid-substituted epicatechin glycosides from Parabarium
huaitingii [J]. Planta Med, 2009, 75(1): 1-5.
[2] Zhu F, Lin YC, Zhou SN. Anthraquinone derivatives isolated
from marine fungus #2526 from the South China Sea [J]. Chin
J Org Chem, 2004, 24(9): 1114-1117.
[3] Song ZZ, Jia ZJ. Studies on the chemical constituents of Bu-
pleurum sibiricum Vest [J]. J Lanzhou Univ, 1992, 28(8):
99-103.
[4] He J, Xian J, Song YY, et al. Chemical constituents of the root
of Ampelopsis japonica (Thunb.) Makino [J]. J Shenyang
Pharm Univ, 2008, 25(8): 636-637.
[5] Tan JJ, Jiang SH, Zhu DY. Studies on the chemical constitu-
ents of Pleurospermum lindleyanum [J]. Nat Prod Res Dev,
2005, 17(3): 267-270.
LEI Ting, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 185−187
2011 年 5 月 第 9 卷 第 3 期 Chin J Nat Med May 2011 Vol. 9 No. 3 187

[6] Cui YJ, Liu P, Chen RY. Studies on the active constituents in
vine stem of Spatholobus suberectus[J]. China J Chin Mater
Med, 2005, 30(2): 121-123.
[7] Zhang WX, Bao WF. Studies on the chemical constituents of
Xanthoceras sorbifolia Bunge [J]. Acta Pharm Sin, 2000, 35(2):
124-127.
[8] Zou JH, Yang JS. Study on chemical constituents of Trollius
ledebouri [J]. Chin Pharm J, 2005, 40(10): 733-735.
[9] Zhang ZZ, Guo D, Li CL, et al. Studies on the chemical con-
stituents of Yunnan Wintergreen (Gaultheria yunnanensis) (I)
[J]. Chin Tradit Herb Drugs, 1998, 29(8): 508-510.
[10] Feng WS, Wang YZ, Zhen XK. Structure analysis of chemical
constituents of traditional Chinese medicine [M]. Beijing: Sci-
ence Press, 2008: 150.

毛杜仲藤皮的化学成分
雷 婷 1, 江海燕 2, 胡 颖 1, 岑颖洲 1*
1暨南大学化学系, 广州 510632;
2广东省物料实验检测中心, 广州 510623
【摘 要】 目的：研究毛杜仲藤皮的化学成分。方法：用硅胶, 制备薄层层析等手段进行分离纯化, 根据化合物的理化性
质和光谱数据鉴定结构。结果：分离并鉴定了 9 个化合物, 即大黄素甲醚(1), 延胡索酸(2), 龙胆酸甲酯(3), 丁香酸甲酯(4), 丁香
酸(5), 2, 5-二甲氧基对苯醌(6), 香草酸(7), 3, 4, 5-三甲氧基苯甲酸(8), 6-甲氧基-7-羟基香豆素(9)。结论：所有化合物均首次从该
植物中分离得到。
【关键词】 毛杜仲藤; 化学成分

【基金项目】 国家自然科学基金项目(No. 20772047)

·Information·

High-cited papers of Chinese
Journal of Natural Medicines

Authors Title Year/Volume/ Issue Page Cited by
Guo, Q.-L. Gambogic acid inducing apoptosis in human gastric adenocarcinoma SGC-7901 cells 2004, 2(2) 106-110 18
Gao, S. Studies on the chemical constituents from roots of Lysidice rhodostegia hance 2005, 3(3) 144-147 13
Zhang, G.-N. Studies on chemical constituents of Dendrobium thyrsiflorum rchb. (I) 2004, 2(2) 78-81 13
Chou, G.-X. Isoquinoline alkaloids from Lindera aggregata 2005, 3(5) 272-275 11
Wang, X.-R. Studies on the flavonol constituents of Abelmoschus manihot L. Medic 2004, 2(2) 91-93 11
Xiao, Y.-J. Investigation of picroside IIs impacts on the P450 activities using a cocktail method 2008, 6(4) 292-297 9
Wei, X.-L. Constituents of the barks of Fraxinus chinensis Roxb 2005, 3(4) 228-230 9
Cai, M.-L. Effects of five flavonoids isolated from Epimedium pubescens on osteoblasts in vitro 2004, 2(4) 235-238 9
Wu, M.-H. Studies on the HPLC fingerprints of Fructus Cnidii 2005, 3(2) 106-111 8
Han, Q.-B. Characterization and quantitative analysis of xanthones in gamboges 2006, 4(3) 210-214 7
Xu, D.-R. Primary study on the original problems of danshensu and protocatechuic aldehyde of Salvia miltiorrhiza 2005, 3(3) 148-150 7
Wang, X.-J. Preliminary study on serum pharmacochemistry of Liu Wei Di Huang Wan 2004, 2(4) 219-222 7
Wan, J.-B. Analysis of saponins from Panax notoginseng using pressurized solvent extraction coupled with high performance thin layer chromatography 2004, 2(4) 215-218 7
Zhao, Y. The proceeding of chemical constituents and pharmacological activities of mangrove 2004, 2(3) 135-140 7
Li, P. Studies on the accelerated solvent extraction of Panax notoginseng saponins 2004, 2(3) 157-161 7
Zou, H.-Y. Study on flavonoids from Lysimachia clethroides 2004, 2(1) 59-61 7
Date sources: Scopus