全 文 ：·论　　文·
【Received date】　2004-09-07
【＊Corresponding author】　Wang Qiang , Professor , China Pharmaceu-
tical Universi ty , Tel:025-85391254 , E-mail:qwang49@sohu.com
A New Homo-cholestane Glycoside from Paris polyphylla
var.chinensis
HUANG Yun1 ,WANG Qiang1＊ ,YEWen-Cai1 , CUI Li-Jian2
1Department of Chinese Materia Medica Analysis , China Pharmaceutical University , Nanjing 210038;
2College of Traditional Medicine , Hebei Medical Universty , Shijiazhuang 050091 , China
【ABSTRACT】　AIM:Steroidal saponins were expected to be isolated from Paris polyphylla var.chinensis.METHOD:The
plant material was extracted with 95% EtOH;the crude saponins were chromatographed on a D101 , a silica gel and ODS col-
umn to afford the compound(Ⅰ).RESULT and CONCLUSION:On the basis of chemical methods and spectral evidences ,
compound(Ⅰ), named Parispolyside E , was confirmed as a new steroidal glycoside , possessing a homo-cholestane skeleton with
an aromatized ring E.And its structure was characterized as 3-O-α-L-arabinofuranosyl(1※4)[α-L-rhamnopyranosyl(1※2)]-
β-D-glucopyranosyl-β-D-chacotriosyl-26-O-β-D-glucopyranoside.
【KEY WORDS】　Paris polyphylla var.chinensis;Steroidal glycoside;Homo-cholestane;Parispolyside E
【CLCNumber】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2005)03-0138-03
　　Paris polyphylla var.chinensis , which is a famous
traditional Chinese medicine ,has been used for its an-
tibiotic and anti-inflammatory function , and has also
been used to treat injuries from falls , fractures ,parotitis ,
and hemostasis.Some steroidal saponins isolated from
Paris were reported with hemostatic and antitumor activ-
ity[ 1].
1　Experiment
1.1　Plant Material and Instruments
The roots of Paris polyphylla var.chinensis were
collected in Nantong , Jiangsu province in May 2003 ,
and then air-dried.The identity of plant material was
verified by Prof.Wang Qiang , and a voucher specimen is
kept in Department of Chinese Materia Medica Analy-
sis ,China Pharmaceutical University.
The melting point was obtained on a X-4 apparatus
and uncorrected.NMR spectra were measured in pyri-
dine d5 and recorded at BrukerAM-500MHz spectrome-
ter for 1H NMR , 13C NMR ,HMBC and HMQC.ESI-MS
spectra were recorded on a HP1100 LC/MSD TRAP.
Silica gel(200 ～ 300 mesh)was from Qingdao Ma-
rine Chemical Factory.All reagents were of analytical
grade.
1.2　Extraction and Isolation
Plant material(4 kg)was extracted with 95% E-
tOH , and concentrated in vacuum.The residue was sus-
pended inH2O and the solution was chromatographed on
a D101 macroreticular resin column eluting with H2O ,
40%, 80%, 95%EtOH successively.The 80%EtOH
fraction was concentrated in vacuum to give residue
crude saponins.This residue was chromatographed on a
silica gel and ODS column to afford 6 mg of compound
(Ⅰ).
Compound(Ⅰ)was named Parispolyside E , ob-
tained as an amorphous powder , mp 281 ～ 283 ℃,
[α] 25D-16.0(MeOH).It had the quasimolecular ion peak
at m/z 1023 [ M-H] - in the negative ESI-MS;UV
spectrum showed strong absorptions band at 277 and
336 nm for a benzene ring.TLC acid hydrolysis showed
that sugars in the molecule were glucose , rhamnose and
arabinose.And its structure was determined on the basis
138　　Chin J Nat Med　May.2005　Vol.3　No.3
CJNM
中国天然药物　2005年 5月　第 3卷　第 3期
of the following data.
The
1
H NMR spectrum showed the characteristic
signals at 0.94(3H , s ,H-18),1.11(3H , s ,H-19),2.32
(3H , s ,H-21), 1.05(3H , d , J =6.5 Hz ,H-27),5.35
(1H ,brs ,H-6),7.04(1H ,d , J =7.4 Hz ,H-22′),7.11
(1H ,d , J =7.4 Hz ,H-16′),which suggested the pres-
ence of three tertiary methyls , a secondary methyl , an
olefinic proton , tow aromatic protons , together with four
anomeric protons signals at 4.87(1H , d , J =8 Hz , glu
H-1),4.96(1H ,d , J =7.5 Hz , glu H-1),6.28(1H , s ,
rha H-1), 5.92(1H , s , ara H-1), and a methyl proton
1.78(3H , d , J =6.5 Hz , rha H-6).By extensive analy-
sis 13C NMR(Table 1),HMQC(Table 1)and ESI-MS
(m/z 1023[M-1] -※891[ 1023-132] -※745[ 891-
146] -※583[ 745-162] -)demonstrated that aglycone
moiety was a β-D-chacotriosyl moiety[ 2] and sugars in
the molecule were two β-D-glucopyranosyls , a α-L-
rhamnopyranosyl and a α-L-arabinofuranosyl[ 3] . Its
molecular formula was indicated to be C52H80O20。
Table 1　13CNMR data of β-D-chacotriosyl[ 2] , parispolyside E and HMQC pivotal data of parispolyside E(125 MHz in pyr-d5)
Position
β-D-chacotriosyl
δc
parispolyside
E
δc
(HMQC)
Correlated
δH
Position
β-D-chacotriosyl
δc
parispolyside
E
δc
(HMQC)
Correlated
δH
Position
pari spolyside
E
δc
(HMQC)
Correlated
δH
1 37.4 37.1 19 19.4 19.1 1.11 Rha-1 101.6 6.28
2 30.2 29.9 20 131.3 131.0 2 72.5
3 78.6 77.4 21 14.7 14.4 2.32 3 72.1
4 39.1 38.7 22 139.8 139.5 4 73.9
5 141.1 140.8 23 31.3 31.7 5 69.1
6 121.8 121.5 5.53 24 35.5 35.2 6 18.3 1.78
7 32.5 32.1 25 34.2 33.8 Ara-1 109.4 5.92
8 31.0 30.7 26 75.0 74.7 2 82.4
9 50.6 50.3 27 16.6 17.1 1.05 3 86.5
10 37.2 36.9 16′ 122.9 122.6 7.11 4 77.9
11 21.3 21.0 22′ 127.5 127.1 7.04 5 61.2
12 37.0 36.7 c-3 sugars c-26 sugar
13 47.2 46.9 Glu-1 100.0 4.87 Glu-1 104.6 4.91
14 57.7 57.4 2 77.7 2 75.0
15 32.0 31.0 3 77.4 3 78.2
16 140.8 140.4 4 76.4 4 71.6
17 151.9 151.5 5 77.2 5 78.4
18 17.4 16.3 0.94 6 62.3 6 62.7
　　The HMBC (Figure 1)confirmed the sequence of
sugar chain was 3-O-α-L-arabinofuranosyl(1 ※4)[ α-
L-rhamnopyranosyl(1 ※2)]-β-D-glucopyranosyl-β-D-
chacotriosyl-26-O-β-D-glucopyranoside.
Fig 1　The structure and key HMBC(denotes)correlation of β-D-chacotriosyl and parispolyside E
中国天然药物　2005年 5月　第 3卷　第 3期
CJNM
Chin J Nat Med　May.2005　Vol.3　No.3　139　
　　It is the first time to get the novel steroidal glyco-
side ingredient possessing a homo-cholestane skeleton
with an aromatized ring E from Paris polyphylla
var.chinensis(Franch.)Hara.
Reference
[ 1] 　Li H , Yang XH , Liang HX , et al.The genus Paris(Trilliaceae)[M]
.Bei jing:Science Press ,1998.193-194.
[ 2] 　Chie Tagawa , Masafumi Okawa , Tsuyoshi Ikeda , et al.Homo-
cholestane glycosides from solanum aethiopicum[ J] .TetrahedronLet-
ters , 2003 , 44:4839-4841.
[ 3] 　Mitsuhiko Miyamura , Kimiko Nakano , Toshihiro Nohara et al.Steroi
saponins from Paris polyphylla SM.-supplement1[ J] .Chem Pharm
Bull ,1982 , 30(2):712-718.
华重楼中一个新的类胆甾烷皂苷
黄　芸1 ,王　强1＊ ,叶文才1 ,崔力剑2
1中国药科大学中药分析教研室 ,南京 , 210038;
2河北医科大学中医学院 ,石家庄 050091
【摘　要】　目的:从华重楼 Paris polyphylla var.chinensis中分离活性成分皂苷类化合物。 方法:药材用 95%乙醇提取 ,
提取物经 D101 大孔树脂柱 ,硅胶柱和ODS 柱反复柱层析 , 得到化合物(Ⅰ)。结果与结论:通过化学方法和波谱方法鉴定
该化合物为一个新的类胆甾烷皂苷 ,命名为:Parispolyside E。 该化合物结构为:3-氧-α-L-阿拉伯糖(1※4)[α-L-鼠李糖(1※
2)]-β-D-葡萄糖-β-D-chacotriosyl-26-氧-β-D-葡萄糖苷 , 是在重楼属发现的第一个具有芳香环的类胆甾烷型的皂苷。
【关键词】　华重楼;甾体皂苷;类胆甾烷;Parispolyside E
·国际会议·
天然产物与新药发现和开发国际会议
Natural Products in Drug Discovery &Development
英国　伦敦　(2005年 6月 27 ～ 28日)
　　大会议题:天然产物在药物发现中的应用
多样性合成的模型
高通量筛选
天然药物发现
基因组学和天然药物靶点
微生物遗传学
天然产物数据库的构建
天然产物衍生物
网　　址:http://www.fungi.com/ immc
140　　Chin J Nat Med　May.2005　Vol.3　No.3
CJNM
中国天然药物　2005年 5月　第 3卷　第 3期