全 文 ： 292 Chin J Nat Med July 2012 Vol. 10 No. 4 2012 年 7 月 第 10 卷 第 4 期

Chinese Journal of Natural Medicines 2012, 10(4): 02920294
doi: 10.3724/SP.J.1009.2012.00292
Chinese
Journal of
Natural
Medicines







Chemical constituents of Menispermum dauricum
CHEN Jian-Yong1, XIE Yu-Feng2, ZHOU Tian-Xi1, QIN Guo-Wei1*
1Shanghai Institute of MateriaMedica, Chinese Academy of Sciences, Shanghai 201203, China;
2Guangdong College of Pharmacy, Guangzhou 510006, China
Available online 20 July 2012
[ABSTRACT] AIM: To study the chemical constituents of Menispermum dauricum DC. METHODS: Compounds were isolated by
repeated chromatography on silica gel and Sephadex LH-20. The structures were identified by spectral analysis and comparison with
literature data. RESULTS: Eleven compounds were obtained and identified as dauricumine (1), dauricumidine (2), acutuminine (3),
physcion (4), blumenol C (5), blumenolA (6), N-trans feruloyltyramine (7), vanillin (8), β-sitostenone (9), β-sitosterol (10), and dau-
costerol (11). CONCLUSION: All compounds were known, but isolated from the plant for first time. Compounds 1 and 2 were
chlorine-containing alkaloids obtained from natural source for the first time. The stereochemistry of 3 was determined for first time.
[KEY WORDS] Menispermum dauricum; Chlorine-containing alkaloids; Chemical constituents
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2012)04-0292-03

1 Introduction
The dried rhizome of Menispermum dauricum DC (Me-
nispermaceae), called Bian Fu Ge in Chinese, is one of the
most commonly used traditional Chinese medicines officially
listed in Chinese Pharmacopoeia. The injection of its total
alkaloids has been used clinically for a long time for the
treatment of chronic tracheitis, throat-sore and arthralgia.
Previous investigation revealed the presence ofbisbenzyliso-
quinoline, oxoisoaporphine, aporphine, protoberberine and
naturally rare-occurred chlorine-containing alkaloids[1-3]. For
further searching bioactive substances the rhizome of Menis-
permum dauricum DC was re-investigated and eleven com-
pounds (1-11) were obtained. This paper describes the isola-
tion and identification of chemical constituents of the plan-
trhizome.
2 Experimental
2.1 General
The UV spectra were obtained using a Shimadzu
UV-3000 spectrometer and IR spectra were recorded on a
Perkin-Elmer 599 B spectrometer. CD spectra were measured

[Received on] 18-June-2011
[Research funding] This project was supported by the National
Natural Sciences Foundation of China ( No. 30470187).
[*Corresponding author] QIN Guo-Wei, Prof., Tel: 86-21-
50805853, Fax: 86-21-50807086, E-mail: gwqin@mail.shcnc.ac.cn
These authors have no any conflict of interest to declare.
using a JASCO-600 CD polarimeter. NMR spectra were re-
corded employing either a Bruker AM-400 or a DRX 500
instrument. Low and high-resolution mass spectra were ob-
tained on a Finnigan-450 or a MAT-711 instrument. Column
chromatography was performed with Si gel 60 (Qingdao Ma-
rine Chemical Co., China). TLC was carried out on percolated
Si gel GF254 plates (Qingdao Marine Chemical Co., China)
2.2 Plant materials
The rhizome of Menispermum dauricum was collected
from Anshan, Liaoning Province, China, in May 1999. The
materials were authenticated by Prof. GUO Ji-Xian of School
of Pharmacy, Fudan University. A voucher specimen was
deposited in the Herbarium of Shanghai Institute of Materia
Medica (No. SIMM99051301).
2.3 Extraction and isolation
A finely-cut dried rhizome (20 kg) of Menispermum dau-
ricum DC was extracted three times with boiling ethanol. The
combined extracts were evaporated under reduced pressure
and the residue was dissolved in 2 % aqueous tartaric acid
and the insoluble part was removed by filtration. The acidic
solution was made alkaline by addition of concentrated
NH3·H2O and extracted exhaustively with chloroform (6
times). The chloroform extracts were combined, dried over
K2CO3 and evaporated. The residue was repeatedly chroma-
tographed on a silica gel column and eluted with chloroform
and chloroform-methanol mixtures of increasing polarity to
obtained compounds 1 (25 mg), 2 (100 mg), 3 (15 mg), 4 (35
mg), 5 (25 mg), 6 (20 mg), 7 (25 mg), 8 (35 mg), 9 (80 mg),
10 (100 mg), and 11 (80 mg), respectively.
CHEN Jian-Yong, et al. /Chinese Journal of Natural Medicines 2012, 10(4): 292294
2012 年 7 月 第 10 卷 第 4 期 Chin J Nat Med July 2012 Vol. 10 No. 4 293

3 Identification
Dauricumine (1) Colorless prismatic crystal (acetone):
mp 219−221 ºC; UV max (log ) 244 (4.27), 270 (3.98) nm;
IR vmax (KBr) cm1: 3 462, 2 785, 1 697, 1 655, 1 608, 1 348,
1 232, 1 074; 1H and 13C NMR, see Table 1; EI-MS m/z (rel.
int.): 397 (9) [M]+, 362 (39), 209 (100), 166 (24); HREI-MS
m/z: Calcd. for C19H24ClNO6, 397.129 2, found 397.128 0.
Table 1 1H and 13C NMR data of compounds 1-3 in CDCl3 (, J in Hz)
1 2 3

Position H C H C H C
2 2.38(m), 2.71(m) 51.9 2.78(m),2.96(m) 43.8 2.40(m), 2.71(m) 51.5
3 2.04(m), 2.12(m) 40.7 2.05(m),2.12(m) 42.8 1.60(m), 1.88(m) 40.4
4 2.51(d, 16.0) 2.81(d, 16.0) 48.9 2.28(d,18.1) 2.85(d,18.1) 46.3
2.23(d,16.0)
2.66(d,16.0) 46.7
5 194.2 193.0 193.0
6 138.4 135.7 138.4
7 160.1 161.0 160.1
8 2.29(dd, 6.8, 12.8) 2.65(dd, 11.8, 12.8) 40.4 2.35(m),2.63(m) 46.7
2.38(dd, 6.8, 12.8)
2.86(dd,11.8, 12.8)
9 4.50(dd, 6.8, 11.8) 60.3 4.46(dd, 6.7, 11.7) 59.4 4.33(dd, 6.8, 11.8) 61.5
10 68.2 68.0 64.7
11 4.55(s) 75.3 4.54(s) 75.5 2.65(2H,m) 36.1
12 187.3 187.5 189.2
13 5.33(s) 105.9 5.33(s) 106.0 5.26(s) 105.6
14 202.3 201.5 204.1
15 52.3 51.1 52.6
16 73.8 70.7 73.1
6-OCH3 3.70(s) 60.5 3.74(s) 60.5 3.68(s) 60.3
7-OCH3 4.12(s) 60.7 4.13(s) 61.0 4.10(s) 60.6
12-OCH3 3.91(s) 59.1 3.91(s) 59.1 3.86(s) 58.8
N-CH3 2.34(s) 35.9 2.34(s) 36.1

Dauricumidine (2) Colorless oily product: UV vmax
(log) 244 (4.23), 270 (3.99) nm; IR vmax (KBr) cm1: 3 327,
1 694, 1 670, 1 612, 1 456, 1 352, 1 238, 1 088; 1H and 13C
NMR, see Table 1; EI-MS m/z (rel. int.) 383 (7) [M]+, 348
(38), 329 (9), 195 (100), 167 (3), 152 (18); HREI-MS m/z:
Calcd. for C18H22ClNO6, 383.113 5, found 383.112 8.
Acutuminine (3) Colorless needles (acetone): mp
174−176 ºC; UV (log ) 244 (4.24), 270 (3.95) nm; IR vmax
(KBr) cm-1: 3 435, 2 939, 1 684, 1 632, 1 593, 1 363, 1 321, 1
064; 1H and 13C NMR, see Table 1; EI-MS m/z (rel. int.) :
381 (9) [M]+, 346 (28), 318 (7), 209 (100), 166 (19), 149 (20);
HREI-MS m/z: Calcd. for C19H24ClNO5, 381.134 3, found
381.134 3.
Physcion (4) Yellow crystals (acetone), mp 203−205 ºC;
1H NMR (CDCl3, ): 2.43 (3H, s, CH3), 3.92 (3H, s, OCH3),
6.65 (1H, d, J = 2.6 Hz), 7.05 (1H, d, J = 1.0 Hz), 7.32 (1H, d,
J = 2.6 Hz), 7.58 (1H, d, J = 1.0 Hz), 12.1 (1H, s, OH), 1.23
(1H, s, OH); 13C NMR (CDCl3, ): 22.1, 56.0, 106.7, 108.1,
110.2, 113.6, 121.2, 124.4, 133.1, 135.2, 148.4, 162.5, 165.1,
166.5, 181.9, 190.7; EI-MS m/z: 284 (base peak), 254, 226,
210, 181, 151, 120.
Blumenol C (5) Colorless oil, IR vmax (KBr) cm1: 3 419
(OH), 1 716 (C=O), 1 653 (C=C); 1H NMR (CDCl3, ): 0.98
（3H, s, CH3), 1.02 (3H, s, CH3), 1.17 (3H, d, J = 6.3 Hz,
CH3), 1.95 (3H, s, =C-CH3), 5.78 (1H, s, C=CH-); EI-MS m/z:
210 (M+), 195, 177, 150, 135, 123, 108 (base peak), 95, 89[4].
Blumenol A (6) Colorless oil, IR vmax (KBr) cm1: 3 369
(OH), 1 710 (C=O), 1 662 (C=C); 1H NMR (CDCl3, ): 1.01
(3H, s, CH3), 1.07 (3H, s, CH3), 1.29 (3H, d, J = 7.4 Hz,
CH3-9), 2.22 (1H, d, J = 17 Hz), 2,44 (1H, d, J = 17 Hz),
4.38 (1H, m), 5.89 (1H, s); 13C NMR (CDCl3, ): 18.9, 22.9,
23.7, 24.0, 41.2, 49.7, 67.9, 79.0, 126.8, 129.1, 135.8, 163.1,
198.2; EI-MS m/z: 206 (M − H2O)+, 178, 151, 123 (base
peak), 111, 78[5].
N-trans feruloyltyramine (7) Colorless crystal, mp
144−145 ºC; IR vmax (KBr) cm1: 3 334 (OH, CONH), 1 652
(O=CNH), 1 591, 1 513(aromatic); 1H NMR (CD3COCD3, ):
7.14 (1H, d, J = 15.6 Hz), 7.17 (1H, d, J = 1.8 Hz), 7.04-7.08
(3H, m), 6.84 (1H, d, J = 8.0 Hz), 6.76 (2H, d, J = 8.0 Hz),
6.51 (1H, d, J = 15.6 Hz), 3.84 (2H, t, J = 7.3 Hz), 2.75 (2H, t,
J = 7.3 Hz); 13C NMR (CD3COCD3, ): 166.5, 156.3, 148.6,
148.3, 140.3, 130.4, 130.0, 127.6, 122.2, 119.2, 115.7, 115.6,
111.1, 55.8, 41.5, 35.2; EI-MS m/z: 313 (M+), 193, 192, 177
(base peak), 145, 120, 107[6].
Vanillin (8) White needle, mp 81−83 ºC, IR vmax (KBr)
cm1: 3 377 (OH), 1 670 (CH=O), 1 593, 1 514 (aromatic);
1H NMR (CDCl3, ): 3.95 (3H, s, OCH3), 6.30 (1H, s), 7.01
(1H, d, J = 8.5 Hz), 7.42 (2H, m), 9.80 (1H, s); EI-MS m/z:
151 (M+−1, base peak), 123, 93, 81.
β-Sitostenone (9) Colorless oil, 1H NMR (CDCl3, ):
CHEN Jian-Yong, et al. /Chinese Journal of Natural Medicines 2012, 10(4): 292294
294 Chin J Nat Med July 2012 Vol. 10 No. 4 2012 年 7 月 第 10 卷 第 4 期

1.11 (3H, s, CH3), 1.19 (3H, s, CH3), 5.62 (1H, s, ethylenic);
13C NMR(CDCl3, ): 11.9, 17.4, 18.7, 19.0, 21.0, 23.1, 24.2,
26.1, 28.2, 29.2, 29.7, 32.0, 32.9, 33.0, 35.6, 36.1, 38.6, 39.6,
42.4, 45.8, 53.8, 55.8, 56.0, 123.7, 171.8, 199.7.
β-Sitosterol (10) by direct comparison with authentic
sample.
Daucosterol (11) by direct comparison with authentic
sample.

4 Results and Discussion
Natural compounds containing halogens in higher plants
are rare. The roots of Manispermum dauricum were reported
to have several chlorine-containing alkaloids including acu-
tumine and acutumidine[2]. Further feeding experiments using
36Cl showed that the root culture produced four 36Cl-labering
alkaloids. They included known acutumine and acutumidine
as well as new dauricumine (1), the C-11 epimer of acutu-
mine and new dauricumidine (2), the C-11 epimer of acutu-
midine[7]. In our study alkaloids 1 and 2 were obtained from
natural plant materials for first time.
Acutuminine (3) was only isolated as a minor component
from the leaves of Manispermum dauricum in 1969. At that
time its structure was suggested mainly by 1H NMR and
EIMS. In our study 3 was isolated from the plant rhizome and
its 1H and 13C NMR data were unambiguously assigned by
1H-1HCOSY, HMQC, and HMBC experiments. The CD
curves of 3 was almost the same as those of 2, both having a
positive Cotton effect near 260 nm and a negative Cotton
effect near 310 nm. Thus the absolute configuration around
ethanamine bridge of 3 was the same as that of 2. In NOESY
spectrum, strong correlations of H-9 with H-8 and H-3
suggested -configuration for H-9; and correlations of H-11
with H-9 and H-3 suggested the stereochemistry of
five-numbered spiro-ring was the same as that of 2.
Compounds 4-11 were isolated from the plant rhizome
for the first time. Their structures were identified by spectral
analysis and comparison with the literature.
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蝙蝠葛中的化学成分
陈建勇 1, 谢郁峰 2, 周天锡 1, 秦国伟 1*
1中国科学院上海生命科学院上海药物研究所, 上海 201203;
2广东药学院药科学院, 广州 510006
【摘 要】 目的：研究中药蝙蝠葛的化学成分。方法：应用硅胶和凝胶反复柱层析进行分离, 分得成分用波谱分析和理化
性质对照进行结构鉴定。结果：分离鉴定出 11 种成分, 分别为 dauricumine (1), dauricumidine (2), acutuminine (3), physcion (4),
blumenol C (5), blumenolA (6), N-trans feruloyltyramine (7), vanillin (8), β-sitostenone (9), β-sitosterol (10), 和 daucosterol (11)。结论：
含氯生物碱 1 和 2 为首次从天然来源中分得, 含氯生物碱 3 的 NMR 数据和立体结构为首次报道, 化合物 4-11 均为首次从本植物
中分到。
【关键词】 蝙蝠葛; 含氯生物碱; 化学成分

【基金项目】 国家自然科学基金 (No. 30470187) 资助项目