全 文 ：
化学成分

Two new monoglycosides from Polycarpon prostratum
DING Zhong- tao, YANG Xue-qiong, BAO Zh-i juan, YE Jing-ru
( Department of Chemistr y, Yunnan University, Kunming 650091, China)
Abstract: Object
To study the chemical const ituents from the w hole plants of Poly carp on p rostr atum
( Forssk. ) Aschers. et Schwein. ex Aschers
Methods
The compounds w ere isolated and purified on silica gel
column chromatog raphy, their structures were identified by spect roscopic methods
Results
Two new mono-
g lycosides, named prost ratosides I and J were isolated from the ethyl acetate ext ract , their st ructures were deter-
m ined to be 3- O-
- L-arabinopyranosy-l 16
-hydroxy-22
-acetoxy-saikogenin E (
) and 3- O-
- L-arabinopyra-
nosy l saikogenin F (
) , respect ively
Conclusion
Compound
and
are tw o new triterpenoid saponins

Key words: Poly carp on p rost ratum ( Forssk
) Aschers
et Schw ein
ex Aschers
; Caryophyllaceae;
triterpeno id saponin; prost ratosides I and J
多荚草中的两个新单糖苷
丁中涛,杨雪琼,保志娟,叶静茹

(云南大学 化学系, 云南 昆明
650091)
摘
要:目的
对石竹科植物多荚草 Polycar p on p r ostr atum 的化学成分进行研究。方法
采用硅胶柱层析进行分
离和纯化,通过波谱分析进行结构鉴定。结果
从其乙酸乙酯萃取部分分离得到了两个新的柴胡皂苷类化合物:
prostratosides I 和 J。通过波谱方法分别鉴定其结构为 3- O-
- L-arabinopyr anosy-l 16
-hydroxy-22
-acetoxy-saikogenin
E (
) 和 3- O-
- L-arabinopyranosyl saikogenin F (
)。结论
化合物
和
均为新化合物。
关键词:多荚草; 石竹科;三萜皂苷; 多荚草皂苷 I 和 J
中图分类号: R284
1


文献标识码: A


文章编号 : 0253 2670( 2003) 05 0388 03


We previously reported the isolat ion and st ruc-
tural elucidat ion of eight new triterpenoid saponins
( named prost ratosides A - H ) [ 1-3] and three new
cyclic pept ides ( named polycarponin A- H)
[ 4, 5]
from
the whole plants of Polycar pon p r ostratum
( Forssk
) Aschers
et Schw ein
ex Aschers
Our
Further invest ig at ion on the EtOAc soluble f ract ion of
this plant led to the isolat ion of tw o new monoglyco-
sides, named prostratosides I and J (
,
)
In this
paper, w e report the isolation and st ructural elucida-
t ion of these two compounds

1
Results and discussion
Prost ratoside I (
) w as obtained as w hite pow-
der
Its FAB-MS gave a [ M - H] - ion at m/ z 645

On acid hydrolysis, only L-arabinose w as detected as
the sugar component
T he 1HNMR spectrum exhibit-
ed the presence of eight methyl groups at
0
92,
0
96, 1
00, 1
05, 1
08, 1
29, 1
70, 1
99 ( 3H
each, s) , two olefinic methine signals at
5
99 ( d,
J= 10
5 Hz, H-11) and 5
67 ( dd, J= 10
5, 2
8
Hz, H-12) , and an anomeric proton at
4
77 ( d,
J= 7
2 Hz,H-1
)
T he 13CNMR spect ral data of

was shown in table 1. The 13CNMR and DEPT spec-
tra showed the anomeric carbon resonances at

107
4
And the presence of a carbonyl signal at

170
5, tw o olef inic methane carbons at
132
3 ( C-
11) and 131
5 ( C-12) , tw o oxy-methane carbons at

70
8 ( C-16) and 77
0 ( C-22) , an oxymethylene

388
中草药
Chinese T raditional and Herbal Drugs
第 34 卷第 5 期 2003年 5月

收稿日期: 2002-08- 12基金项目:云南省中青年学术和技术带头人后备人才培养基金资助课题( Yp0024)作者简介:丁中涛( 1968- ) ,男,汉族,云南人,博士,云南大学化学系教授,主要从事天然药物化学和分析化学方面的研究工作,已发表研究论文 40余篇。
Tel: ( 0871) 5033726
E-mail: ztding@ ynu. edu. cn
carbon at
76
7 ( C-28) , a quaternary carbon at

84
8 ( C-13) , and eight methyl carbons at
16
3,
18
2, 18
3, 19
6, 21
0, 25
1, 27
9 and 33
3 in-
dicated that compound
had the same aglycone as
prost ratoside B, a tetraglycoside isolated f rom the
same plant[ 1]
The signals at C-16 and C-28 are in
relat ive low field, indicating the presence of an
-OH
at C-16[ 6] . T he 1HNMR signal of H-22 (
5
28, dd,
J = 12
4, 5
6Hz) , suggestedH-22 to be an axial H

T herefore, the st ructure of prost ratoside I (
) w as
determined to be 3- O-
- L-arabiopyranosy-l 16
-hy-
droxy-22
-acetox y-saikogenin E

R1 R 2 R3

CH3
-OH
-OAc

CH2OH
-OH H
Fig
1
Structures of prostratosides I (
) and J (
)
Prost ratoside J (
) w as obtained as w hite pow-
der and revealed the [ M- H ] - ion peak at m/ z 603
in the negat ive FAB-M S
A 13CNMR spectral com-
parison w ith
show ed that
also had the same
linked sugar moiety, different structurally from

only in it s aglycone
The 1HNMR spectrum of

showed six angular methyl groups at
0
91, 0
96,
0
98, 1
00, 1
13 and 1
41, tw o olefinic proton sig-
nals at
6
00 ( 1H , d, J= 10
6 Hz, H-11) and 5
66
( 1H , dd, J = 10
6, 2
5 Hz, H-12) , and an anomer-
ic proton at
4
74 ( 1H, d, J= 8
0 Hz, H-1
)
The
13
CNMR spect ral data of
was shown in T able 1.
T he 13CNMR and DEPT spect ra show ed an anomeric
carbon resonance at
107
6
tw o olefinic signals at

132
1 and 131
2 corresponding to tw o methine car-
bons ( C-11 and C-12) , two methylene carbon signals
at
73
1 ( C-28) and 64
6 ( C-23) , a quaternary car-
bon signal at
84
2 ( C-13)
The signals at C-16 (

64
0) and C-28 are in relat ive high field, indicat ing
the presence of a
-OH at C-16[ 6]
T he above data re-
vealed that the aglycone of
was saikogenin F[ 7]

T herefore, the structure of
was characterized as 3-
O-
- L-arabinopy ranosy-l saikogenin F

Table 1
13CNMR data for prostratosides I (
)
and J (
) in C5D5N (125 MHz)
Position
 Position



1
38
6
38
7

20
33
3
31
5
2 26
6 26
0 21 42
1 34
7
3 88
6 82
0 22 77
0 25
9
4 40
2 43
7 23 27
9 64
6
5 55
4 47
6 24 16
3 13
1
6 18
0 17
7 25 18
3 18
7
7 31
9 31
7 26 19
6 20
1
8 42
1 42
4 27 18
2 21
1
9 52
9 53
2 28 76
7 73
1
10 36
4 36
3 29 33
3 33
6
11 132
3 132
1 30 25
1 23
9
12 131
5 131
2
OAC 170
5
13 84
8 84
2 21
0
14 44
2 45
8 1
107
4 107
6
15 35
2 36
3 2
72
9 73
1
16 70
8 64
0 3
74
6 74
7
17 49
5 47
1 4
69
5 69
5
18 51
0 52
3 5
66
7 66
9
19 37
6 37
8
2
Experiment
2
1
General experimental procedures
NMR spectra
w ere obtained on Bruker DRX-500 MHz spectrome-
ters
A VG Auto Spec-3000 spectrometer w as used to
record FAB-M S spectrum 200- 300 meshes and 300
- 400 meshes silica gel and Diaion HP-20 w ere used
for column chromatography

2
2
Plant material
The whole plants of P
p ros-
t ratum ( Forssk
) Aschers et Schw ein ex Aschers.
w ere collected in Xishuangbanna, Yunnan Provin-ce,
China, in July 1997
The botanical identif icat ion was
made by senior engineer Wang Hong, f rom
Xishuangbanna Tropical Botanical Garden, the Ch-i
nese Academy of Sciences

2
3
Ex tract ion and isolat ion
T he plant material
( 17
8 kg) w as ex tracted with hot ethanol four t imes
to af ford an EtOH ex tract that was suspended in w a-
ter, and ext racted with ethy l acetate and n-butanol,
respect ively
The EtOAc residue ( 168
0 g ) was
chromatog raphed on Diaion HP-20 w ith a H 2O-
MeOH gradient system ( 1
0
0
1)
The fract ion e-
luted w ith 70% MeOH was further subjected to silica
gel ( CHCl3-M eOH= 9
1) co- lumn chromatography
to af ford prost ratosides I (
, 18 mg) and J (
, 12
mg) , respect ively

2
4
Identification
Prostratoside I (
) :

389
中草药
Chinese T raditional and Herbal Drugs
第 34 卷第 5 期 2003年 5月
C37H58O9, w hite pow der
FAB-MS [ M - H ] - m/
z : 645: 1HNMR ( C5D5N, 500 MHz ) ;
0
92,
0
96, 1
00, 1
05, 1
08, 1
29, 1
70, 1
99 ( 3H
each, s) , 4
77 ( 1H , d, J= 7
2 Hz, H-1ara ) , 5
99
( 1H , d, J= 10
5 Hz, H-11) , 5
67 ( 1H , dd, J=
10
5, 2
8 Hz, H-12) , 5
28 ( 1H, dd, J= 12
4, 5
6
Hz, H-22)

Prost ratoside J (
) : C35H56O8, w hite powder

FAB-MS [ M - H ]
-
m/ z : 603;
1
HNMR ( C5D5N,
500 MHz) ;
0
91, 0
96, 0
98, 1
00, 1
13, 1
41
(3H each, s) , 4
74 ( 1H, d, J = 8
0 Hz, H-1ara ) ,
6
00 ( 1H, d, J= 10
6 Hz, H-11) , 5
66 ( 1H , dd,
J = 10
6, 2
5 Hz, H-12)

Acknowledgements: We would like to express our thanks
to Prof
Zhou Jun, an academician of the Chinese Academy of
Sciences, and Prof
Tan Ning-hua fo r their suggestive ideas and
direct help in our experiment

References:
[ 1]
Ding Z T , Zhou J , He Y N, et al
New triterpenoid saponins
from Polycarpon p rostratum [ J]
Ac ta Bot S in ( 植物学报 ) ,
2000, 42( 3) : 306-310

[ 2]
Ding Z T , Zhou J, Dai H F, et al
St ructures of prost ratosides
D and E [ J]
A cta Bot Yunnan ( 云南植物研究) , 2001, 23
( 2) : 261-265

[ 3]
Ding Z T , Zhou J, Tan N H, et al
T hree new saikosap-onin-
like compounds from Polycarp on p rostr atum [ J]
Chin Chem
L et t (中国化学快报) , 2001, 12( 8) : 705-708

[ 4]
Ding Z T , Zhou J, Cheng Y X, et al
A new cyclopept ide from
Polycarp on p rostratum [ J]
Chin Chem L ett ( 中国化学快
报) , 2000, 11( 7) : 593- 594

[ 5]
Ding Z T , Zhou J, Tan N H, et al
Cyclopeptides f rom Poly-
carpon prost ratum [ J]
Acta Bot Sin (植物学报 ) , 2001, 43
( 5) : 541-544

[ 6]
Jia Q, Zhang R Y
Advances in chemical study on saponins in
plants of Bupleurum L
[ J]
Acta Phar m S in ( 药学学报 ) ,
1989, 24( 12) : 961-971

[ 7]
Mori F, M iyase T , Ueno A
Oleanne-t riterpens saponins from
Cl inop odium chinense var
parv if l orum [ J]
Phytochemist ry ,
1994, 36( 6) : 1485-1488

水甘草化学成分的研究
王爱国,冯孝章

(中国医学科学院 中国协和医科大学药物研究所, 北京
100050)
摘
要:目的
研究水甘草甲醇提总生物碱的化学成分。方法
利用离子交换树脂、大孔吸附树脂、硅胶柱层析分
离纯化,根据化合物的光谱数据鉴定其结构。结果
从水甘草甲醇提总碱中分得 3 个化合物, 分别鉴定为 rhazid-i
genine,
,水甘草酸( amsonic acid,
) ,反式芥子酸甲酯( trans-sinapic acid methylester,
)。结论
化合物
为新化
合物,
和
为首次从该植物中得到。
关键词:水甘草; 吲哚生物碱;水甘草酸
中图分类号: R284
1


文献标识码: A


文章编号 : 0253 2670( 2003) 05 0390 03
Studies on chemical constituents of Amsonia sinensis
WANG A-i guo, FENG Xiao-zhang
( Institute of Materia Medica, CAMS & PUMC, Beijing 100050, China)
Abstract: Object
To study the chem ical const ituents of alkaloids of A msonia sinensis Tsiang ext racted
w ith methanol
Methods
Compounds w ere separated by exchange resin, macroporous resin and silica gel co-l
umn chromatography
Their structures were elucidated by spect roscopic analysis
Results
Three compounds
w ere isolated f rom total alkaloids of A
sinensis ex tracted w ith methanol
T hey w ere ident if ied as: rhazidige-
nine (
) , amsonic acid (
) , t rans-sinapic acid methy lester (
)
Conclusion
Compound
is a new one,
and compound
and
are obtained from this plant for the f irst t ime

Key words: A msonia sinensi s Tsiang; indole alkalo id; amsonic acid


水甘草 A msonia sinensis Tsiang 是我国特有的 夹竹桃科水甘草属植物,分布于长江流域,民间用作

390
中草药
Chinese T raditional and Herbal Drugs
第 34 卷第 5 期 2003年 5月

收稿日期: 2002-08- 14基金项目:国家自然科学基金资助项目( 29372086)作者简介:王爱国( 1963- ) ,男,北京人,助理研究员,主要从事天然产物研究工作。
Tel: ( 010) 63165231
* 通讯作者
T el: ( 010) 63165226
E-mail : FengXZ@ Imm
ac
cn