全 文 ：·有效成分·
A new triterpenoid saponin from Lysimachia candida
ZHANG Xiao-rong , PENG Shu-lin, WANG Ming-kui , Ding Li-sheng

( Chengdu Institute o f Biolog y , Chinese Academy o f Sciences, Chengdu Sichuan 610041, China )
Abstract: Object　 To investiga te the chemical constituents f rom the who le plant o f Lysimachia candi-
da Ldl. . Methods　 The consti tuents w ere isolated and puri fied on silica g el co lumn chromatog raphy.
Their st ructures w ere elucidated by chemica l and spect roscopic evidence. Results　 A triterpenoid saponin,
named candido side A (Ⅰ ) , w as iso lated f rom the ex t ract of n-BuOH. Its st ructure was show n to be 3β ,
16α-dihydroxy-olean-12-en-28-al-3-O-β-D-g lucopyranosy l-23-O-α-D-ribofuranoside. Conclusion　 Candi-
doside A w as a new tri terpenoid saponin.
Key words: Lysimachia candida Ldl. ; triterpenoid saponin; candidoside A
从单条草中分得一个新的三萜皂苷
张晓 ,彭树林 ,王明奎 ,丁立生*
(中国科学院成都生物研究所 ,四川 成都　 610041)
摘　要:目的　对报春花科珍珠菜属药用植物单条草 Lysimachia candida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 ,通过波谱和化学方法进行结构鉴定。 结果　从正丁醇萃取部分分离出 1个三萜皂苷类化合
物 ,结构鉴定为: 3β , 16α-二羟基齐墩果 -12-烯 -28-醛 -3-O-β -D-吡喃葡萄糖基 -23-O-α-D-呋喃核糖苷 ,命名为单条草
苷甲 (Ⅰ )。 结论　单条草苷甲是新结构的三萜皂苷。
关键词: 单条草 ;三萜皂苷 ;单条草苷甲
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2002) 06 0481 03
　　 The plant of Lysimachia candida Ldl. ( Prim-
ulaceae) , a Chinese folk medicine, has long been
used to t reat detoxication and promote blo od ci rcu-
lation. We repor ted one new tri terpenoid saponin
and 12 known compounds f rom the methano lic ex-
tracts
[1 ]
. This paper deals w ith the separation and
st ructure elucidation of ano ther new triterpenoid
saponin, named as candidoside A (Ⅰ ) .
1　 Results and Discussion
Candido side A (Ⅰ ) wa s obtained as amor-
phous powder. It s fo rmula was determined a s
C41 H66O13 by HR-FAB-M S a t m /z 767. 455 7
( [M+ H ]
+ , calcd. 767. 458 2) . The IR spect rum
exhibi ted abso rptions at 3 432 ( O H ) and 1 710
cm
- 1 ( C= O) . Acid hydro lysis of Ⅰ yielded glu-
cose and ribose on T LC. In the posi tiv e FAB-M S
ofⅠ , besides the quasi-molecular ion peak, frag-
ment ion peaks a t m /z 605 [M- g lc+ H ]
+
and 455
[ M - glc- rib - H2O+ H]
+
were observ ed. The
EI-M S of acetylatedⅠ show ed fragment ion peaks
at m /z 259 [rib ( O Ac) 3 ]
+
and 331 [g lc ( OAc) 4 ]
+
,
suggesting that g lucose and ribose moieties should
be terminal monosaccharide. In the
1
HNM R and
13
CNM R spect ra, the presence of sev en quaternary
ca rbon atoms and the chemical shi ft s of C-12 atδ
123. 6 and C-13 a tδ143. 6 w ere characteristics of a
Δ12-oleanene skeleton. Acid hydro lysis o fⅠ gave
aglycone Ⅰ a, who se 13 CNM R spect rum disclosed
the presence of th ree hydro xy lated carbons (δ
78. 1, 73. 0, 73. 5) . Th e signal o f C-3 (δ78. 1)
suggested an equato rial posi tion for the 3-OH.
Comparing the
13
CNMR signals o f Ⅰ a w ith
·481·中草药　 Ch inese Tradi tional and Herbal Drugs　 2002年第 33卷第 6期
收稿日期: 2000-10-12
作者简介:张晓 ( 1973-) ,女 ,四川巴中市人 ,中国科学院成都生物研究所 ,助研 ,硕士 ,主要从事天然产物研究。
* 通讯作者: Tel: ( 028) -5223843　　 E-mai l: ls ding@ cib. ac. cn
those of o leanolic acid
[2 ]
, C-5 of Ⅰ a was shi fted
upfield to δ49. 8. According to the rule of steric
ef fect, a hydroxy l must be linked to C-23 (δ
73. 5) . The signal o fδ205. 7 (d) and 73. 1 (d) in-
dicated an aldehyde and a tertia ry hydroxyl group.
Except fo r C-17, C-22 and C-28, th e
13
CNMR sig-
nals ofⅠ a w ere almost identical w ith those of 3β ,
16α, 23, 28-tet rahydroxy-o lean-12-ene[3 ] , w hich
revealed tha tα-OH and -CHO were linked to C-16
and C-17, respectiv ely. This conclusion was fur-
ther suppo rted by the HMBC spect rum ofⅠ . The
aldehyde pro ton a tδ9. 49 ( -CHO) co rrela ted wi th
the carbons a tδ73. 1 ( C-16) , 51. 5 ( C-17) , and
40. 8 ( C-18) . In the 13 CNMR spect rum ofⅠ , the
signals of C-3 and C-23 w ere shi f ted downfield toδ
85. 6 and 78. 3 respectiv ely as compared to signals
o f i t s aglyconeⅠ a. According to the rule o f g lyco-
sylation shif t , C-3 and C-23 ofⅠ must link wi th a
monosaccharide, respectiv ely. The
1
HNM R spec-
trum of Ⅰ had tw o anomeric proton signals atδ
5. 27 ( d, J= 6. 8 Hz) and 5. 17 ( d, J= 7. 8 Hz) and
i ts
13
CNMR spect ral da ta indicated the presence of
terminal β -D-g lucopyrano sy l uni t andα-D-ribofu-
ranosyl uni t
[4 ] . Based on the HMBC spect rum of
Ⅰ , the proton at δ4. 01 ( H-3) had co rrela tion
w ith C-1 (δ 105. 4) o f g lucose and the hydroxy-
methyl pro ton atδ3. 87 ( H-23) had a cross-peak
w ith C-1 (δ 103. 7) of ribo se. It w as confi rmed
that gluco se w as a ttached to the C-3 posi tion and
ribose to C-23. Thus, the structure ofⅠ was elu-
cidated to be 3β , 16α-dihydroxy-o lean-12-en-28-al-
3-O-β-D-g lucopyranosy l-23-O-α-D-ribofuranoside.
The key HMBC co rrela tions for Ⅰ ( see Fig. 1) ,
chemical shif t s ofⅠ andⅠ a (see Table 1) .
2　 Experimental
2. 1　 General experimenta l pro cedures: IR spec-
trum was measured on a Nicolet MX-1 spect rome-
ter as a pressed KBr disk. NM R spect ra were
recorded on Bruker AP-300 and DRX-500 M Hz
spect rum was TM S as the internal standard. M S
spect ra w ere measured on a V G AutoSpec-3000
mass spect rometer. Silica g el w ith 200-300 mesh
w as used fo r column ch romatog raphy.
2. 2　 Plant material: The who le plant o f L . candi-
Fig. 1　 The key HMBC correlations forⅠ
Table 1　 Chemical shif ts of compoundsⅠ ( in C5D5N ,
500MHz for 1H and 125 MHz for 13C) and
Ⅰ a ( in C5D5N , 75 MHz) ( J: Hz)
C, H
atom
13CNM R of
Ⅰ *
13CNM R of
Ⅰ a
1HNM R of
Ⅰ
HMBC
( H to C)
1 　 38. 9 ( t ) 　　 38. 2
2 27. 3 ( t ) 26. 2
3 85. 6 ( d) 78. 1 4. 01, dd C: 1, 5, Glc-1
4 37. 2 ( s ) 41. 8
5 51. 6 ( d) 49. 8
6 17. 7 ( t ) 18. 4
7 32. 7 ( t ) 32. 7
8 40. 0 ( s ) 39. 7
9 47. 0 ( d) 46. 6
10 37. 1 ( s ) 36. 8
11 23. 6 ( t ) 23. 1
12 123. 6 ( d) 123. 7 5. 45, b rs C: 18　　
13 143. 6 ( s ) 142. 1
14 40. 9 ( s ) 41. 4
15 35. 5 ( t ) 34. 6
16 73. 1 ( d) 73. 0
17 51. 5 ( s ) 50. 7
18 40. 8 ( d) 40. 3
19 46. 9 ( t ) 46. 2
20 30. 8 ( s ) 30. 4
21 34. 9 ( t ) 35. 4
22 23. 6 ( t ) 23. 3
23 78. 3 ( t ) 73. 5 3. 88, d , J= 10. 3 C: 3, 4, Rib-1
3. 86, d , J= 10. 3
24 13. 8 ( q) 11. 4 1. 06, s C: 3, 4, 5, 23
25 16. 6 ( q) 17. 1 0. 797, s C: 1, 5, 9, 10
26 17. 4 ( q) 17. 6 0. 739, s C: 7, 8, 9, 14
27 27. 1 ( q) 26. 9 1. 65, s C: 8, 13, 14, 15
28 205. 7 ( d) 204. 7 9. 49, s C: 16, 17, 18
29 33. 3 ( q) 32. 9 0. 977, s C: 19, 20, 21
30 24. 2 ( q) 23. 9 1. 00, s C: 19, 20, 21
　　* Sugar moieties of Ⅰ : Glc: 105. 4 ( d) , 75. 2 ( d ) , 78. 5 (d ) ,
70. 5 (d ) , 78. 4 ( d ) , 62. 7 ( t ) ; Rib: 103. 7 ( d ) , 71. 2 ( d ) , 71. 7
( d ) , 83. 8 (d ) , 64. 4 ( t )
da was collected in Mianyang , Sichuan Province,
China and identified by Professo r Xiao Shun-
chang , Chengdu Institute o f Biolog y , Chinese A-
cademy o f Sciences.
·482· 中草药　 Ch inese Tradi tional and Herbal Drugs　 2002年第 33卷第 6期
2. 3　 Ex traction and isola tion: The dried powder
( 7. 25 kg ) was ex t racted three times wi th M eOH
fo r ten days each time at room temperature. Af ter
removal of the so lv ent. the residue w as suspended
in H2O and successiv ely ex t racted wi th pet roleum
ether ( bp 60℃～ 90℃ ) , EtO Ac and n -BuOH.
The n-BuOH ex tracts ( 108 g ) w ere subjected to
si lica gel ( CHCl3-MeOH= 35∶ 1) co lumn chro-
ma tog raphy to obtain six f ractions. Fraction six th
w as ch romatog raphed over silica g el eluted wi th
CHCl3-M eOH ( 20∶ 1 ) to af fo rd compound Ⅰ
( 30 mg ) .
2. 4　 Identification: Compound Ⅰ white powder,
IRνKBrmax ( cm- 1 ): 3 432, 2 946, 2 936, 1 710, 1 112,
1 075, 1 040. HR-FAB-M S [ M + H ]
+
m /z:
767. 455 8 ( C41 H67O15 , calcd. 767. 458 2) . FAB-
M S ( - ) m /z: 765 [ M - H ]
- , 603 [ M - g lc ]
- .
FABM S (+ ) m /z: 767 [M+ H ]
+
, 605 [M- g lc+
H ]
+
, 455 [M- g lc- rib- H2O+ H]
+
.
Hydroly sis o f Ⅰ : Compound Ⅰ ( 8 mg ) hy-
dro lyzed wi th 0. 5 mo l /L H2 SO4 ( 5 mL, EtO H-H2O
= 1∶ 1) in boiling w ater ba th fo r 4 h. Af ter re-
moval of EtO H under reduced pressure, the mix-
ture w as ex t racted wi th chlo roform th ree times.
The organic layer wa s evapo ra ted to dryness to
giveⅠ a ( 5 mg) .
Acetylation o fⅠ : CompoundⅠ ( 2 mg ) w as
acetylated w ith Ac2O-py ridine ( 1∶ 2, 0. 75 mL) at
room tempera ture fo r 48 hours to yield acetate of
Ⅰ . EI-M S ( m /z): 331, 259.
References:
[ 1 ]　张晓 ,彭树林 ,肖顺昌 ,等 . 单条草的皂苷成分 [ J ].植物学
报 , 1999, 41( 5): 534-536.
[ 2 ]　 Shashi B M, Asish R K. 13 CNMR spect ra of pentacyclic t r-
i terpenoids— a compilation and som e salient featu res [ J].
Ph ytochemis try, 1994, 37( 6): 1517-1575.
[ 3 ]　 Amoros M , Gi rre R L. St ructu re of two an tiviral trit erpene
saponins f rom Anagal lis a rvensis [ J]. Phy toch emis t ry, 1987,
26( 3): 787-791.
[4 ]　廖　循 ,李伯刚 ,丁立生 ,等 . 复伞银莲花中的三萜皂苷 [ J ].有
机化学 , 2001, 21( 4): 299-304.
山楂化学成分研究
孙敬勇 ,杨书斌 ,谢鸿霞 ,李贵海 ,邱海霞
(山东省中医药研究所 ,山东 济南　 250014)
摘　要: 目的　从山里红 Crataegus pinnatif ida var. major的成熟干燥果实寻找中药山楂中的专属性成分和降血
脂的活性成分。 方法　利用多种柱色谱技术进行分离和纯化 ,根据 UV、 IR、 EI-M S、 FAB-M S、 1 HNM R、 13 CNM R、
HMBC、 HMQC和 13CGATE等波谱数据分析鉴定结构。 结果　从山里红成熟果实中分离鉴定了 6个化合物 ,分别
为: 5, 7, 4′-三羟基黄酮 -8-C-α-L-吡喃鼠李糖基 -( 1→ 2) -β-D-吡喃葡萄糖苷 (Ⅰ ) ,即牡荆素鼠李糖苷 ( vitexin rham-
noside) ,金丝桃苷 ( hyper oside,Ⅱ ) ,枸橼酸 ( citric acid,Ⅲ ) ,牡荆素 ( v itex in,Ⅳ ) ,槲皮素 ( quer cetin,Ⅴ ) ,熊果酸 ( ur-
so lic acid,Ⅵ )。结论　化合物Ⅰ 为中药山楂中的专属性成分 ,首次由山里红果实中分得 ,化合物Ⅱ为山楂中的降血
脂主要黄酮成分。
关键词: 山里红 ;牡荆素鼠李糖苷 ;金丝桃苷
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2002) 06 0483 04
Studies on chemical constituents from fruit of Crataegus pinnat if ida
SUN Jing-yong , YANG Shu-bin, X IE Hong-xia, L I Gui-hai, QIU Hai-xia
( Shandong Institute o f TCM , Jinan Shandong 250014, China )
Abstract: Object　 To look fo r the proprietary consti tuent and the consti tuents wi th blood lipid regu-
lating ef fect f rom th e dried f rui t of Crataegus pinnat if ida Bge. v ar. major N. E. Br. Methods　 Various
column chromatog raphic techniques w ere employed fo r isolation and purification of the consti tuents. UV ,
·483·中草药　 Ch inese Tradi tional and Herbal Drugs　 2002年第 33卷第 6期
收稿日期: 2001-08-23
基金项目: “九五”国家重点科技攻关项目 ( 96-903-02-03)
作者简介:孙敬勇 ( 1970-) ,男 ,山东省人 ,助理研究员 , 1992年毕业于上海医科大学药学院药物化学专业获理学学士学位。主要从事中药
新药开发研究。 Tel: ( 0531) 2968470-3027