全 文 ：152. 6( C-3′, C-5′) , 137. 2( C-4′) , 102. 8( CG-1× 2) ,
77. 2 ( CG -5× 2) , 76. 5( CG -3× 2) , 74. 2( CG-2× 2) ,
70. 0( CG-4× 2) , 61. 0( CG-6× 2) , 56. 4( 4× OCH3 ) ,
数据与文献报道一致 [3 ]。
山奈酚 -3-O-β -D-吡喃葡萄糖苷 (Ⅲ ): 1 HNMR
δ8. 03 [ H-2′, H-6′( 2H, d, J= 8. 8 Hz) ] , 6. 87 [ H-3′,
H-5′( 2H, d,J= 8. 8 Hz) ] , 6. 42( H-8) , 6. 19( H-6) ,
5. 44( 1H, d, J = 7. 6 Hz) ; 13 CNMRδ177. 4 ( C-4) ,
164. 3( C-7) , 161. 2( C-5) , 159. 9( C-4′) , 156. 4 ( C-
2) , 156. 3( C-9) , 133. 3 ( C-3) , 130. 8( C-2′, C-6′) ,
120. 9 ( C-1′) , 115. 1 ( C-3′, C-5′) , 104. 0 ( C-10 ) ,
98. 7( C-6) , 93. 7( C-8) , 101. 1( CG-1, 3-O-Glc) , 77. 4
( CG -5) , 76. 5( CG-3) , 74. 2( CG -2) , 70. 0( CG-4) , 60. 9
( CG-6) ,数据与文献报道一致 [4 ]。
7-O-α-L-吡喃鼠李糖基 -山奈酚-3-O-β-D-吡喃
葡萄糖苷 (Ⅳ ): 1 HNMRδ8. 08 [ H-2′, H-6′( 2H, d,
J= 8. 8 Hz ) ] , 6. 90 [ H-3′, H-5′( 2H, d, J = 8. 7
Hz) ] , 6. 81 ( H-8) , 6. 44 ( H-6) , 5. 54 ( 1H, br. s,
Rha ) , 5. 47( 1H,d, J= 7. 2 Hz) , 1. 10( 3H, d, J= 6. 4
Hz) ;
13
CNMRδ177. 6( C-4) , 161. 6( C-7) , 160. 8( C-
5) , 160. 0 ( C-4′) , 156. 7 ( C-2) , 156. 0( C-9) , 133. 5
( C-3) , 130. 9( C-2′, C-6′) , 120. 7( C-1′) , 115. 1( C-
3′, C-5′) , 105. 6 ( C-10) , 98. 4 ( C-6) , 94. 2 ( C-8) ,
100. 8( CG-1, 3-O-Glc ) , 77. 4 ( CG-5) , 76. 4 ( CG -3) ,
74. 2 ( CG-2) , 70. 2( CG-4) , 60. 8( CG-6) , 99. 3( CR-1,
7-O-Rha ) , 71. 6 ( CR-4) , 70. 1( CR-3) , 70. 0( CR-2) ,
69. 7( CR-5) , 17. 8( CR-6) ,数据与文献报道一致 [5 ]。
山奈苷 (Ⅴ ): 1HNM Rδ7. 78 [ H-2′, H-6′( 2H, d,
J = 8. 4 Hz ) ] , 6. 90 [ H-3′, H-5′( 2H, d, J = 8. 5
Hz) ], 6. 78 ( H-8 ) , 6. 45 ( H-6 ) , 5. 54 ( 1H, br. s,
Rha′) , 5. 29 ( 1H, br. s, Rha) , 1. 01( 3H, d, J = 6. 4
Hz) , 0. 79( 3H, d, J= 6. 0 Hz) ;
13
CNM Rδ177. 8( C-
4) , 161. 6( C-7) , 160. 9( C-5) , 160. 0 ( C-4′) , 157. 6
( C-2) , 156. 0 ( C-9) , 134. 5 ( C-3) , 130. 5 ( C-2′, C-
6′) , 120. 3( C-1′) , 115. 3( C-3′, C-5′) , 105. 7( C-10) ,
98. 4 ( C-6 ) , 94. 5 ( C-8) , 101. 8 ( CR-1, 3-O-Rha ) ,
71. 5( CR-4) , 70. 5( CR-3) , 70. 2( CR-2) , 69. 9( CR-5) ,
17. 8( CR-6) , 99. 3 ( CR′-1, 7-O-Rha ) , 71. 1( CR′-4) ,
70. 3 ( CR′-3) , 70. 2( CR′-2) , 69. 7( CR′-5) , 17. 3( CR′-
6) ,数据与文献报道一致 [5 ]。
致谢:中国科学院昆明植物研究所植化室仪器
组测试各项波谱。
References:
[1 ]　 Editorial Of fice of Nat ional Chines e Herbal Medicine Col lec-
tion. Collect ion of N ational Chinese Herbal Med icine (全国中
草药汇编 ) [M ] . Bei jing: People s Medical Publi shing House,
1992.
[2 ]　 Jiangsu New Medical College. Dict ionary of Ch inese Materia
Med ica (中药大辞典 ) [M ]. Shanghai: Shanghai Science and
Tech nology Pub lish er, 1977.
[3 ]　 Macrae W D and Tow ers G HN. Biological activi tes of lig nans
[ J ]. Phytoch emistr y, 1984, 23( 6): 1207-1211.
[4 ]　 M arkh am K R, Ternal B, Stanley R, et al . 13CNM R s tudies
of fl avonoids-Ⅲ [ J] . Tetrahed ron , 1978, 34( 3): 1389-1398.
[5 ]　 Pauli G F. High er order and sub sti tuen t ch emical shi f t ef fects
in the p roton NM R of glycosides [ J] . J Na t P rod , 2000, 63
( 6): 834-839.
Chemical constituents from root of Glycyrrhiza uralensis
ZHU Xu-min, DI Ying-tong , PEN G Shu-lin, WANG Ming-kui, DIN G Li-sheng

( Chengdu Institute of Bio lo gy , CAS, Chengdu 610041, China)
Abstract: Object　 To investig ate the chemica l consti tuents f rom the ro ots of Glycyrrhiza uralensis
Fisch. Methods　 The constituents w ere isola ted on no rmal and reversed silica g el co lumn chroma tog raphy
and thei r st ructures w ere identified by spectral evidence. Results　 A new o leanane-type t ri terpenoid
saponin and tw elv e known compounds, including two triterpenoid saponins, tw o cumarins and eight
f lav onoids, w ere isolated. Conclusion　 The new compound was elucidated as 3-O-[β -D-( 6-methy l) g lu-
curonopy ranosyl ( 1→ 2) -D-g lucuronopy rano syl ]-24-hydroxy-glabrolide on the basis of ESI-M S, 1HNM R,
13
CNMR, HMQC and HMBC spect ral evidence.
·198· 中草药　 Chinese T raditional and Herbal Drug s　第 34卷第 3期 2003年 3月
收稿日期: 2002-08-12基金项目:中国科学院生物科技特别支持项目 ( ST Z-97-3-08)作者简介:丁立生 ( 1958- ) ,男 ,博士 ,研究员 (博士生导师 )。 主要从事天然有机化学研究。
Tel: ( 028) 85223843　 E-mai l: ls ding@ cib. ca. cn
Key words: Glycyrrhiza uralensis Fisch; t ri terpenoid saponins; 3-O-[β -D-( 6-methy l ) g lucuronopy-
ranosyl ( 1→ 2) -D-glucuronopy ranosyl ]-24-hydroxy-glabrolide
乌拉尔甘草中的化学成分
朱绪民 ,邸迎彤 ,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　分析乌拉尔甘草 Glycyrrhiza uralensis的化学成分。方法　采用正、反相硅胶柱层析分离 ,应用波谱
方法进行结构鉴定。结果　从甘草中共分离出 3个三萜皂苷、 2个香豆素和 8个黄酮类化合物 ,其中一个三萜皂苷
为新化合物。结论　通过 ESI-M S, 1 HNM R, 13CNMR, HM QC和 HM BC分析 ,将新三萜皂苷的结构鉴定为 3-O-[β -
D-葡萄糖醛酸甲酯 -( 1→ 2) -β -D-葡萄糖醛酸 ]-24-羟基 -甘草内酯。
关键词: 乌拉尔甘草 ;三萜皂苷 ; 3-O -[β-D-葡萄糖醛酸甲酯 -( 1→ 2) -β-D -葡萄糖醛酸 ] -24-羟基 -甘草内酯
中图分类号: R283. 3　　　文献标识码: A　　　文章编号: 0253 2670( 2003) 03 0198 04
　　 As a pa rt o f inv estigation on g lycy rrhiza , a fa-
mous Chinese herbal medicine, a new o leanane-
type t ri terpenoid saponin w as isolated f rom the
roots o f Glycyrrhiza uralensis Fisch. Tw elve
known compounds, including tw o triterpenoid
saponins, tw o cuma rins and eight f lav onoids were
also isola ted. This paper deals wi th the iso la tion
and structure elucidation of these compounds.
Fig. 1　 Sturcture and key HMBC correlat ion of I
1　 Results and discussion
Compound I w as obtained as whi te powder,
[α]25D+ 3. 5. Its molecular fo rmula w as assigned a s
C43 H62O17 by HR-ESI-M S ( [ M + H ]
+
m /z
851. 402 9, calc. 851. 406 5) . The IR spect rum of
I show ed the presence o f hydroxyl ( 3 447 cm
- 1 )
and carbony l g roups ( 1 753 cm
- 1
) .
1
HNM R and
13
CNMR spectra ( Table 1) of I suggested i t w as a
24-hydroxy-glabrolide 3-O-glycoside
[ 1, 2]
. Acidic
hydroly sis of I on TLC indica ted that suga r moiety
w as composed o f glucuronic acid.
13
CNM R signals
due to the sugar moiety suggested it w as glu-
curonopy ranosyl ( 1→ 2) -glucuronopyanosy l[2 ] and
the anomeric pro ton signals atδH 4. 97 ( d, J= 7. 6
Hz) , and 5. 59 ( d, J= 7. 2 Hz) indica ted that the
two glucuronopyranosyls w ere inβ-o rienta ted. Sig-
nals a tδC 52. 1 andδH 3. 82 show ed one of the g lu-
curonopyranosy l w as methy l esteri fied and the
f ragment ion at m /z 659 [M - 191 ]+ in negativ e
ion ESI-M S /M S analysis rev ealed that the terminal
glucuronopy ranose w as esterified. It was proved
by the correlation in HMBC spect rum. Therefo re,
the st ructure o f I was elucidated as 3-O-[β -D-( 6-
methy l ) glucuronopyranosyl ( 1→ 2) -D-g lucuron-
opyranosy l ]-24-hydroxy-glabrolide show n in Fig.
1. Ana lysis o f HMQC and HMBC spectra allow s
proton and carbon signals assigned in Table 1.
Compound I can not be detected f rom the ho t
w ater ex t ract of the ro ots o f G. uralensis by
HPLC-M S ( ODS co lumn, MeOH/H2O) . So i t may
be an arti fact due to the use of methanol in co lumn
chromato graphy and the o riginal naturally occur-
ring compound should be 3-O-[β -D-g lucuronopy-
rano syl ( 1→ 2) -D-g lucuronopy ranosyl ]-24-hydrox-
yg labro lide which was detected in curde saponin by
HPLC-M S ( ODS column, M eOH/H2O).
Based on directed compa rison wi th the pub-
lished spect ral data and authentic samples, the
known compounds w ere identi fied as liqui ri tig enin,
liqui ri tin [3 ] , pinocembrin [4 ] , i soliquiritig enin [5 ] ,
liqui ri tig enin-7, 4′-diglucoside[6 ] , ononin [7 ] , gly cy-
rol, i sog lycyrol
[ 8] , licof lav onol
[9 ] , lico ricidin
[10 ] ,
gly cy rrhizic acid
[11 ]
and licorice-saponin E2
[2 ] , re-
spectiv ely.
2　 Experiment
·199·中草药　 Chinese T raditional and Herbal Drug s　第 34卷第 3期 2003年 3月
Table 1　 1HNMR and 13CNMR data of compound I ( pyridine-d5 )
C δC δH　　 C δC δH C δC　 δH　　
　 1 39. 6 2. 95 16 　 25. 9 1. 06, 1. 44, 2H, br 1′ 　 104. 5 4. 97, 1H, d, J = 7. 6
2 26. 6 1. 36 17 35. 7 2′ 82. 3 4. 24, 1H
3 89. 8 3. 45, 1H, dd, J = 11. 6, 4. 5 18 44. 6 2. 26, 1H, br 3′ 77. 7 4. 26, 1H
4 44. 4 19 40. 8 1. 71, 2H, br 4′ 72. 9 4. 50, 1H
5 56. 1 0. 83, 1H 20 42. 1 5′ 77. 9 4. 54, 1H
6 18. 5 1. 29, 2. 13, 2H, br 21 38. 1 1. 94, 2H, br 6′ 172. 2
7 33. 5 1. 21, 1. 36, 2H, br 22 83. 9 4. 16, 1H, d, J = 5. 8 1″ 105. 8 5. 59, 1H
8 44. 9 23 23. 0 1. 44, 3H, s 2″ 75. 7 4. 22, 1H
9 61. 9 2. 38, 1H, s 24 63. 3 3. 67, 4. 33, J= 11. 6 36″ 77. 3 4. 46, 1H
10 37. 1 25 16. 5 1. 20, 3H, s 4″ 72. 7 4. 36, 1H
11 198. 9 26 18. 5 0. 95, 3H, s 5″ 77. 7 4. 47, 1H
12 130. 0 5. 66, 1H, s 27 22. 3 1. 32, 3H, s 6″ 170. 2
13 164. 3 28 24. 0 0. 88, 3H, s OCH3 52. 1 3. 82, 3H
14 45. 0 29 20. 3 1. 15, 3H, s
15 25. 2 1. 54, 1. 63, 2H, br 30 179. 6
2. 1　 General experimental procedures: Optical ro-
tation w as mea sured wi th PE-241 polarimeter.
Spect ral da ta w ere obtained using the fo llowing ap-
paratus: IR spect rum w ith a Nicolet MX-1 spec-
trometer; N MR spect ra wi th a Va rian Unity Ino-
va-400 spect rometer wi th tet ramethylsi lane
( TM S) as an internal standard; HR-ESI-M S spec-
trum with a Bruker Daltonics ApexⅡ mass spec-
trometer and M S /M S and HPLC-M S analy sis wi th
a ThermoFinnig an LCQ
DECA
mass spect rometer.
Silica g el ( 170-200 mesh ) and Loba r LiChroprep
RP-18 column w ere used fo r column chromatog ra-
phy.
2. 2　 Plant ma terial: The ro ots of G. uralensis
Fisch. ( Gancao ) w ere collected in 1999 from
Chi feng , Neimeng , China.
2. 3　 Ex traction and isolation: The ai r-dried and
powdered gly cy rrhiza ( 2 kg ) w as on ult rasonic ex-
traction wi th N H3-EtOH-H2O ( 0. 5∶ 10∶ 89. 5)
fo r three times. Af ter removal of the solv ent , the
sy rup was suspended in H2O and ex tracted wi th
ethyl acetate fo r three times. Then the H2O frac-
tion w as adjusted to pH= 2 by adding 70% H2 SO4 ,
and centrifuga lized to separate the precipi ta te. By
using silica g el ( pet ro leum /acetone or CHCl3-
MeOH) and RP-18 ( M eOH-H2O) co lumns, liquir-
itig enin ( 300 mg ) , liqui ri tin ( 8 g ) , pinocembrin
( 12 mg ) , isoliqui ri tig enin ( 10 mg ) , liqui ri tigenin-
7, 4′-dig lucoside ( 100 mg ) , ononin ( 240 mg ) ,
g lycyro l ( 350 mg ) , isoglycy rol ( 120 mg ) , li-
cof lav ono l ( 100 mg ) and lico ricidin ( 380 mg ) were
isola ted f rom ethy l acetate ex t ract and I ( 10 mg ) ,
gly cy rrhizic acid ( 2 g ) and lico rice-saponin E2 ( 30
mg ) f rom the precipitate, respectiv ely.
2. 4　 Identification
Compound Ⅰ : white powder, [α]25D + 3. 5
( CHCl3 -CH3OH= 1∶ 5, c= 0. 002) . IRνKBrmax cm- 1:
3 447, 2 949, 1 753, 1 658, 1 085, 1 048; ESI-
M S-M S ( - ) m /z: 659 [ M - g luCH3 ]
-
( 849→
659) ; HR-ESI-M S (+ ) m /z: 851. 402 9 ( [ M+
H ]
+ , C43 H63 O17 , calc: 851. 406 5) , 467. 312 7
( [ M - ( g luCH3 - g luO ) ]
+
, C30 H43 O4 , calc:
467. 316 ) .
1
HNMR and
13
CNMR data w ere show n
in Table 1.
References:
[ 1]　 Shu Y H, Zhao Y Y, Zhang R Y. Isolat ion and id en tif ication
of t rit erp ene sapogenins f rom Glycyr rhiza uralensis Fisch.
[ J ]. Acta Pharm Sin , 1985, 20( 3): 193-197.
[2 ]　 Kitagaw a I, Hori K, Sakagami M , et al . Saponin and sa-
pogenol. XLV III. On the con sti tuen ts of th e roots of Gly -
cyrrh iza uralensis Fisch f rom north eastern Ch ina. ( 2 ) .
Lico rice-saponins D3, E2, F3, G2, H2, J2, and K2 [ J].
Chem Pharm Bul l , 1993, 41( 8): 1337-1345.
[3 ]　 Yang S L, Liu Y L. Chemical const ituents of Glycyr rhiza in-
f lata Bat [ J ]. Acta Bot Sin, 1988, 30( 2): 176-182.
[ 4]　 Fukui H, Goto K, Tabata M . Tw o ant imicrobial fl avanones
f rom th e leaves of Glycyrrhiza glabra [ J ]. Chem Pharm
Bul l , 1988, 36( 10) : 4174-4176.
[ 5 ]　 Zhu D Y, Song G Q, Jiang F X, et al . Studies on ch emical
cons ti tuen ts of Glycyrrh iza uralensis Fis ch—— The s truc-
tures of i solicoflavonol and glycycoumarin [ J] . Acta Chem
Sin , 1984, 42: 1080-1084.
[6 ]　 Yabara S, Nishioka I. Flavonoid glucosides f rom licorice
[ J] . Phytochem istry , 1984, 23( 9): 2108-2109.
[7 ]　 Nakanishi T, Inada A, Kam bayashi K, et al . Flavonoid g ly-
cosides of th e roo ts of Glycyr rhiza uralensi s [ J ]. Phytochem -
ist ry , 1985, 24( 2): 339-341.
·200· 中草药　 Chinese T raditional and Herbal Drug s　第 34卷第 3期 2003年 3月
[8 ]　 Shiozaw a T, Urata S, Kinoshi ta T, et al . Revis ed s t ructu res
of glycyrol and is oglycyrol, cons ti tuen ts of the root of Gly-
cyrrh iza ura lensis [ J] . Chem Pharm Bul l , 1989, 37 ( 8 ):
2239-2240.
[9 ]　 Saitoh T, Kinoshi ta T, Shibata S. Flavonols of licorice root
[ J] . Chem Pharm Bul l , 1976, 24( 6): 1242-1245.
[10 ]　 Chang X R, Xu Q H, Zhu D Y, et al . The is olation and
st ructu ral elucidation of li coneolignan f rom G. uralensis [ J].
Acta Pha rm Si , 1983, 18( 1): 45-50.
[ 11 ]　 Zapesochnaya G G, Zvonk ova EN, Ku rkin V A, et al . Some
propert ies of glycyrrh izic acid [ J] . Chem Nat Comp , 1994,
30( 6): 720-726.
木芙蓉叶化学成分研究
姚莉韵 ,陆　阳 ,陈泽乃
(上海第二医科大学 化学教研室 ,上海　 200025)
摘　要: 目的　研究木芙蓉叶 Hibiscus mutabilis的化学成分。方法　采用硅胶柱、 C18反相柱、聚酰胺柱色谱分离纯
化 ,通过理化常数测定和光谱分析鉴定化合物的结构。结果　从木芙蓉叶中分离得到 10个化合物。根据波谱分析
和理化数据 ,鉴定出其中 9个化合物分别为:二十四烷酸 ( tetraco sanoic acid, Ⅰ )、β-谷甾醇 (β-sito stero l, Ⅱ )、胡萝
卜苷 ( daucoster ol, Ⅲ )、水杨酸 ( salicylic acid, Ⅳ )、大黄素 ( emodin, Ⅴ )、芸香苷 ( rutin, Ⅵ )、山奈酚 -3-O-β-芸香糖
苷 ( kaempfero l-3-O -β -rutinoside, Ⅶ )、山奈酚 -3-O-β-刺槐双糖苷 ( kaempfero l-3-O-β -robinobino side, Ⅷ )及山奈酚 -
3-O-β -D-( 6-E -对羟基桂皮酰基 ) -葡萄糖苷 〔 kaempfero l-3-O -β -D-( 6-E -p-hydroxycinnamoy l) -glucopyr ano side,
Ⅸ 〕。结论　除Ⅱ和Ⅵ 外 ,其他化合物均为首次从该植物中分离得到。
关键词: 木芙蓉叶 ;黄酮苷 ;甾醇
中图分类号: R283. 3　　　文献标识码: A　　　文章编号: 0253 2670( 2003) 03 0201 03
Studies on chemical constituents of Hibiscus mutabilis
YAO Li-yun, LU Yang , CHEN Ze-nai
( Depar tment o f Chemistry , Shanghai Second Medical Univ e rsity , Shanghai 200025, China)
Abstract: Object　 To study the chemical constituents o f Hibiscus mutabil is L. Methods　 Isolation
and purification w ere carried out on si lica gel, o r polyamide column chromato g raphy etc. Consti tuents w ere
identi fied and structurally elucidated by physicochemical proper ties and spect ral analysis. Results　 Ten
compounds w ere obtained, nine o f them were determined as tetracosanoic acid (Ⅰ ) , β-si to sterol (Ⅱ ) ,
daucosterol (Ⅲ ) , salicy lic acid (Ⅳ ) , emodin (Ⅴ ) , rutin (Ⅵ ) , kaempferol-3-O-β -rutinoside (Ⅶ ) ,
kaempferol-3-O-β-robinobinoside (Ⅷ ) and kaempferol-3-O-β -D-( 6-E-p -hydroxycinnamoyl ) -glucopy ra-
noside (Ⅸ ) . Conclusion　 All compounds a re isolated f rom the plant for the frist time exceptⅡ and Ⅵ .
Key words: Hibiscus mutabil is L. ; flavonoid g lycosides; sterol
　　木芙蓉 Hibiscus mutabilis L. 属锦葵科木槿属
植物 ,其花、叶和根均可入药。具有清热解毒、消肿排
脓、凉血止血之功用 ,在民间广泛用于治疗痈肿疮
疖。文献记载该药外用和口服有很好的抗炎、消肿作
用 ,可以治疗阑尾炎、腮腺炎 ,也可以治疗痛风性关
节炎、丹毒和灼伤 [1 ]。我校附属瑞金医院魏指薪老中
医的经验方“消肿散”应用于临床 40多年 ,对丹毒、
急性软组织损伤、痛风、滑膜炎等引起的红、肿、热、
痛有非常好的疗效 ,其中主要药物就是木芙蓉叶。药
理实验已证实 ,木芙蓉叶水提取物有较强的抗炎、镇
痛作用 ,且无明显胃肠道刺激作用 [2 ]。已报道木芙蓉
叶的化学成分只有芦丁 (芸香苷 ) [ 3]和 β-谷甾醇 [4 ]。
我们对木芙蓉叶的化学成分进行了系统分离 ,从中
分离到 10个化合物 (Ⅰ ～ Ⅹ ) ,鉴定了其中 9个化合
物。 分别为 4个黄酮苷化合物:芸香苷 ( rutin, Ⅵ )、
山奈酚 -3-O-β -芸香糖苷 ( kaempferol-3-O-β -ruti-
·201·中草药　 Chinese T raditional and Herbal Drug s　第 34卷第 3期 2003年 3月
收稿日期: 2002-09-18基金项目:上海市高等学校科学技术发展基金项目 ( 98ZD33)作者简介:姚莉韵 ( 1966- ) ,女 ,上海第二医科大学化学教研室副教授 ,硕士 ,主要从事中草药的化学成分研究及含量测定。
Tel: ( 021) 63846590-776464