全 文 ：草珊瑚中一个新的苯基丙二醇类化合物*
段营辉1,2, 李摇 畅3, 戴摇 毅1,4, 姚新生1,3,4**
(1 暨南大学中药及天然药物研究所, 广东 广州摇 510632; 2 暨南大学中西医博士后流动站, 广东 广州摇 510632; 3 沈阳药
科大学中药学院, 辽宁 沈阳摇 110016; 4 广东省中药药效物质基础及创新药物研究重点实验室, 广东 广州摇 510632)
摘要: 从金粟兰科植物草珊瑚 (Sarcandra glabra) 全株的水提取物中分离得到一个新的苯基丙二醇类化合
物 (2S)鄄3, 3鄄二鄄(4鄄羟基鄄3鄄甲氧基苯基)鄄丙鄄1, 2鄄二醇 (1), 以及一个已知化合物, 银线草内酯 E (2), 并
利用 NMR、 MS、 旋光值等波谱学技术鉴定其了结构。
关键词: 草珊瑚; 金粟兰科; 苯基丙二醇
中图分类号: Q 946摇 摇 摇 摇 摇 摇 摇 文献标识码: A摇 摇 摇 摇 摇 摇 摇 文章编号: 2095-0845(2012)02-208-03
A New Phenylpropanediol from Sarcandra glabra (Chloranthaceae)
DUAN Ying鄄Hui1,2, LI Chang3, DAI Yi1,4, YAO Xin鄄Sheng1,3,4**
(1 Institute of Traditional Chinese Medicine and Natural Products, Jinan University, Guangzhou 510632, China; 2 Integrated
Traditional Chinese and Western Medicine Postdoctoral Station, Jinan University, Guangzhou 510632, China; 3 School of Traditional
Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, China; 4 Guangdong Province Key Laboratory
of Pharmacodynamic Constituents of TCM and New Drugs Research, Jinan University, Guangzhou 510632, China)
Abstract: A new phenylpropanediol, (2S)鄄3, 3鄄di鄄(4鄄hydroxy鄄3鄄methoxyphenyl)鄄propane鄄1, 2鄄diol (1), along
with a known compound, shizukanolide E (2) were isolated from the water extract of the whole plants of Sarcandra
glabra. The structure was elucidated on the basis of extensive NMR, MS, and ORD spectral analysis.
Key words: Sarcandra glabra; Chloranthaceae; Phenylpropanediol
摇 Sarcandra glabra (Thunb. ) Nakai (Chloranthac鄄
eae), widely distributed in southern parts of China
and southeast Asian, is an important traditional Chi鄄
nese medicine used for antibacterial, antititumor and
anti鄄inflammation effects (Takeda et al., 1993). Previ鄄
ous phytochemical investigations on this plant repor鄄
ted the isolation of flavonoids, sesquiterpenes, trit鄄
erpenoids, coumarins, and other phenolics (Hu et
al., 2009; Li et al., 2006; Tsui and Brown, 1996;
Takeda et al., 1993; Huang et al., 2010). The mar鄄
keted products related to Sarcandra glabra suchu as
Fufang Caoshanhu Hanpian, Qingre Xiaoyanning
Jiaonang, were extracted with water, so a phyto鄄
chemical investigation on the water extract was nec鄄
essary. In our continuation studies on this medicinal
plant, a new compound (1) and a known compound
(2) were isolated. Herein, we reported the isolation
and structure identification of this new compound.
Results and discussion
Compound 1 was obtained as white amorphous
powder, [琢] 25. 8D +20. 0 (c. 0. 9, CH3OH). Its mo鄄
lecular formula was established as C17H20O6 by HR鄄
ESI鄄MS at m / z 319. 1183 [M鄄H] - ( calcd for C17
植 物 分 类 与 资 源 学 报摇 2012, 34 (2): 208 ~ 210
Plant Diversity and Resources摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 DOI: 10. 3724 / SP. J. 1143. 2012. 11162
*
**
Foundation items: Chinese Pharmacopeia Commission (TS鄄61) and Guangdong Technology Significant Project (2004Z1鄄E5011)
Author for correspondence; E鄄mail: tyaoxs@ jnu. edu. cn
Received date: 2011-11-10, Accepted date: 2012-02-01
作者简介: 段营辉 (1983-) 男, 博士, 主要从事中药及天然药物活性成分研究。
H19O6, 319. 1182), indicating eight degrees of un鄄
saturation. The IR spectrum displayed absorption
bands for hydroxy groups (3 391 cm-1) and phenyl
rings (1 604 cm-1, 1 518 cm-1 and 1 464 cm-1 ).
The 1H NMR spectrum of 1 (Table 1) revealed the
presence of two sets of 1, 2, 4鄄trisubstituted aromat鄄
ic signals [啄H 6. 52 (1H, d, J = 1. 8 Hz, H鄄2忆),
6. 53 (1H, d, J=8. 0 Hz, H鄄5忆), 6. 41 (1H, dd,
J= 8. 0, 1. 8 Hz, H鄄6忆); 6. 60 (1H, d, J = 1. 6
Hz, H鄄2义), 6. 55 (1H, d, J = 8. 0 Hz, H鄄5义),
6. 50 (1H, dd, J=8. 0, 1. 6 Hz, H鄄6义)], two me鄄
thine signals [啄H 4. 67 (1H, d, J=8. 0 Hz, H鄄3);
2. 83 (1H, m, H鄄2)], one oxygenated methylene
signal [啄H 3. 84 (1H, dd, J = 10. 5, 5. 8 Hz, H鄄
1a), 3. 71 (1H, dd, J = 10. 5, 6. 9 Hz, H鄄1b)],
in addition to two methoxy signals [ 啄H 3. 62, 3. 61
(each 3H, s)]. In the 13C NMR and DEPT spectra
of 1, seventeen carbon signals were observed, in鄄
cluding twelve sp2 aromatic carbon [ 啄C 146. 6 伊 2,
144. 9, 144. 5, 135. 4, 132. 0, 121. 3, 119. 2, 114. 6,
114. 4, 113. 4, 111. 2] arising from two benzene
rings, three sp3 carbons [ 啄C 75. 2, 63. 3, 54. 7],
and two methoxy carbons [啄C 55. 5, 55. 4]. On the
basis of the HSQC and 1H鄄1H COSY spectra of 1, a
spin system proton signals [ H鄄3 ( 啄H 4. 67), H鄄2
(啄H 2. 83) and H鄄1a (啄H 3. 84), H鄄1b (啄H 3. 71)]
was established. The results suggested the presence
of propyl moiety in the structure of 1. The propyl
moiety was linked to the C鄄1忆 and C鄄1义 of benzene
rings on the basis of the HMBC correlations of H鄄3 /
C鄄1忆 ( 啄C 132. 0), H鄄2 / C鄄1忆, and H鄄3 / C鄄1义 ( 啄C
135. 4), C鄄2义 (啄C 111. 2), C鄄6义 (啄C 119. 2) (Fig.
1). In the ROESY spectrum, the proton signals of
two methoxy groups at 啄H3. 62 (3H, s) and 3. 61
(3H, s) correlated with H鄄2忆 and H鄄2义, respective鄄
ly, suggesting the two methoxy groups located at C鄄
3忆 (啄C 146. 6) and C鄄3义 (啄C 146. 6). Because the
optical rotation of compound 1 ( [琢] 25. 8D +20. 0, c=
0. 9, CH3OH) was similar to those of (2S)鄄3, 3鄄
diphenylpropane鄄1, 2鄄diol ( [琢] D+48. 0, c= 1. 0,
CH3OH) (Gopishett et al., 2011), suggesting that
the absolute configuration of 1 at C鄄2 was S. Thus,
compound 1 was identified as (2S)鄄3, 3鄄di鄄(4鄄hy鄄
droxy鄄3鄄methoxyphenyl)鄄propane鄄1, 2鄄diol.
The known compound shizukanolide E (2) was
identified on the basis of reported physical NMR and
ESIMS data (Li et al., 2005). The previous phyto鄄
chemical investigations on Sarcandra glabra were
mainly focused on the EtOH extract, the type of new
compound isolated from the water extract was differ鄄
ent from that of EtOH extract. And the studies on
the water extract of this plant made a little contribu鄄
tions to the qualities of the marketed products.
Fig. 1摇 Key HMBC (寅) and ROESY («) correlations of 1
Table 1摇 NMR data for compound 1 in DMSO鄄d6 (400 MHz for 1H)
position 啄H(mult, J ) 啄C(mult) position 啄H(mult, J ) 啄C(mult)
1a 3. 84 (dd, 1H, J=10. 5, 5. 8 Hz) 63. 3 ( t) 1义 135. 4 (s)
1b 3. 71 (dd, 1H, J=10. 5, 6. 9 Hz) 2义 6. 60 (d, 1H, J=1. 6 Hz) 111. 2 (d)
2 2. 83 (m, 1H) 54. 7 (d) 3义 146. 6 (s)
3 4. 67 (d, 1H, J=8. 0 Hz) 75. 2 (d) 4义 144. 9 (s)
1忆 132. 0 (s) 5义 6. 55 (d, 1H, J=8. 0 Hz) 114. 6 (d)
2忆 6. 52 (d, 1H, J=1. 8 Hz) 113. 4 (d) 6义 6. 50 (dd, 1H, J=8. 0, 1. 6 Hz) 119. 2 (d)
3忆 146. 6 (s) 3忆鄄OCH3 3. 62 (s, 3H) 55. 4 (q)
4忆 144. 5 (s) 3义鄄OCH3 3. 61 (s, 3H) 55. 5 (q)
5忆 6. 53 (d, 1H, J=8. 0 Hz) 114. 4 (d)
6忆 6. 41 (dd, 1H, J=8. 0, 1. 8 Hz) 121. 3 (d)
9022 期摇 摇 摇 摇 摇 摇 摇 摇 DUAN Ying鄄Hui et al. : A New Phenylpropanediol from Sarcandra glabra摇 摇 摇 摇 摇 摇 摇 摇 摇 摇
Experimental
General experimental procedures摇 UV spec鄄
tra were measured on a JASCO V鄄550 UV / vis spec鄄
trophotometer. IR spectra were recorded on a JASCO
FTIR鄄400 spectrometer. 1D and 2D NMR spectra
were recorded on a Bruker AV鄄400 spectrometer
(400 MHz for 1H, 100 MHz for 13C). ESI鄄MS data
were recorded on a Finnigan LCQ Advantage MAX
mass spectrometer. HR鄄ESI鄄MS data were deter鄄
mined by an Waters Synapt G2 MS mass spectrome鄄
ter. HPLC was performed on a Gilson system with a
306 pump and a UV / vis鄄152 detector, using a re鄄
versed phase column (21. 2伊250 mm, 5 滋m, Welch
XB鄄C18) at 8 mL / min and monitored at 280 nm.
Open column chromatography (CC) was performed
using silica gel (200 - 300 mesh, Qingdao Marine
Chemical Co. Ltd., Qingdao), ODS (50 滋m, YMC),
and Sephadex LH鄄20 (Pharmacia). Thin鄄layer chrom鄄
atography (TLC) was performed using precoated sil鄄
ica gel plates (silica gel GF254, 1 mm, Yantai) .
Plant Material摇 The plant material was gener鄄
ously provided by Guangzhou Jingxiutang Pharma鄄
ceutical Co. Ltd. (Guangzhou, China), and was i鄄
dentified as the whole plant of Sarcandra glabra by
Professor Guang鄄xiong Zhou (College of Pharmacy,
Jinan University). A voucher specimen (20070910)
was maintained in Institute of Traditional Chinese
Medicine & Natural Products, Jinan University,
Guangzhou 510632 China.
Extraction and Isolation 摇 The whole dried
plants (4. 0 kg) of S. glabra were refluxed with wa鄄
ter twice, for two hours each time. After evaporation
of solvent in vacuo, the residue (446. 4 g) was dilu鄄
ted with water. The filtrate was separated on macro鄄
porous adsorption resin Diaion HP20 using water and
30% , 50% , and 90% EtOH鄄H2 O in sequence to
afford four fractions (parts A鄄D). Part C (42. 6 g)
was chromatographed over ODS column and eluted
with MeOH鄄H2O (9 颐 1 to 0 颐 1) to afford five frac鄄
tions. Fraction 3 was further subjected to Sephadex
LH鄄20 column chromatography using CHCl3 鄄MeOH
(1 颐 1 ) as eluents and finally purified by prep.
HPLC with MeOH鄄H2O鄄HAc (40 颐 60 颐 0. 1) to af鄄
ford the compound 1 (2. 0 mg). Fraction 4 was fur鄄
ther subjected to silica gel column chromatography
eluted with CHCl3 鄄MeOH (9 颐 1) and finally puri鄄
fied by Sephadex LH鄄20 using CHCl3鄄MeOH (1 颐 1)
to yield compound 2 (4. 0 mg).
(2S)鄄3, 3鄄di鄄(4鄄hydroxy鄄3鄄methoxyphenyl)鄄pro鄄
pane鄄1, 2鄄diol (1): C17H20O6, white amorphous pow鄄
der. [琢]25. 8D +20. 0 (c 0. 9, CH3OH). IR (KBr) 淄max
cm-1: 3397, 2937, 1604, 1518, 1464, 1432, 1125,
821. UV (CH3OH) 姿max (log 着): 211 (3. 95), 228
sh (3. 72), 280 (3. 39) nm. 1H NMR and 13C NMR
data see Table 1. Negative ESI鄄MS m / z: 319 [M鄄
H] -, 639 [2M鄄H] -; HR鄄ESI鄄MS m / z: 319. 1183
[M鄄H] - (calcd for C17H19O6, 319. 1182).
Acknowledgments: We thank Jian鄄liang Geng, Tao Shi and
Rong Ding for measuring the HR鄄ESI鄄MS and NMR data.
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