全 文 ：Chem ica l con stituen ts of A can thop anax g racilis ty lus
L IU X iang2qian1, YOO K Chang2soo 2, CHAN G Seung2yeup 3
(11 D epartm ent of Pharm aceu tical Industry, Co llege of Chem istry and Chem ical Engineering, Cen tra l Sou th U niversity,
Chang sha 410008, Ch ina; 21 D epartm ent of Pharm acogno sy, Co llege of Pharm acy, Kyung2H ee U niversity, 1 Hoek i2
Dong, Dongdoemoon2ku, Seou l 1302701, Ko rea; 31 Ko rean Food and D rug A dm in istra t ion, Seou l 1222704, Ko rea)
Abstract: Object　To study the chem ical con st ituen ts of A can thop anax g racilisty lus W 1W 1 Sm ith as
the pu rpo se of study con t inually on p lan ts of A can thop anax (D ecne. et P lanch. ) M iq1 M ethods　T he
leaves, roo ts, and stem bark s of A 1 g racilisty lus w ere ex tracted w ith ho t M eOH and steam dist illa t ion re2
spect ively, and then, separa ted and pu rif ied by co lum n ch rom atograph ies on D iaion H P220P, Ch rom ato rex
OD S, Sephadex L H 220 and silica gel1 A ll compounds w ere iden t if ied on the basis of chem ical and spectra l
analysis including GC2M S, 1D and 2D NM R , M S and IR , o r comparison w ith the repo rted data1 Results　
Six compounds w ere ob ta ined from the roo ts of A 1 g racilisty lus1 T hey are (- ) 2p im ara29 (11) , 152dien2
192o ic acid (É ) , (- ) 2kau r2162en2192o ic acid (Ê ) , d 2sesam in (Ë ) , st igm astero l (Ì ) , Β2sito stero l (Í ) ,
and eleu thero side B (Î ) 1 Conclusion　Compounds É , Ì , and Í are ob ta ined from th is p lan t fo r the
first t im e1
Key words: A can thop anax g racilisty lus W 1W. Sm ith; A raliaceae; chem ical con st ituen t
细柱五加皮化学成分的研究
刘向前1, 陆昌洙2, 张承烨3Ξ
(11 中南大学化学化工学院 制药工程系, 湖南 长沙　410008; 　21 庆熙大学药学院 生药学研究室, 　
韩国 汉城; 　31 韩国食品医药品安全厅, 韩国 汉城)
摘　要: 目的　系统地研究五加属植物细柱五加皮A canthop anax g racilisty lus 的化学成分。方法　用热甲醇分别
对细柱五加皮的根进行提取后, 采用D iaion H P220P, Ch rom ato rex OD S, Sephadex L H 220 和硅胶色谱进行分离纯
化, 通过光谱分析以及直接和标准品对照进行结构确认。结果　从根皮中得到二萜类等 6 个化合物: 五加酸 (É ) ,
异贝壳杉烯酸 (Ê ) , l2芝麻素 (Ë ) , 豆甾醇 (Ì ) , Β2谷甾醇 (Í )和刺五加苷B (Î )。结论　化合物É , Ì , Í 为首次从
该植物中分离得到。
关键词: 细柱五加皮; 五加科; 化学成分
中图分类号: R 28411　　　文献标识码: A 　　　文章编号: 0253 2670 (2004) 03 0250 03
1　 In troduction
A can thop anax g racilisty lus W 1 W 1 Sm ith be2
longs to A can thop anax (D ecne. et P lanch1) M iq1
(A raliaceae) , has been u sed as a trad it ional o rien2
ta l m edicine w ith ton ic, an t irheum atic, longitudi2
nal bone grow th, adap togen ic act ivity, fa t igue,
an t itumo r act ivity and gastric u lcer and p rophylac2
t ic funct ion s fo r ch ron ic b ronch it is hyperten sion,
an t ist ress, ischem ic heart d isease [124 ] 1 A s an en2
dem ic A sian genu s, over 35 species have been dis2 t ribu ted m ain ly no rtheastern A sia including Ch ina,Japan, Ko rea, and in o ther reg ion s, such asBhu tan, India, M ongo lia, M alaysia, N epal, Ph ili2pp ines, R u ssia, T hailand, V ietnam , etc. Som e ofthem w ere also found [5, 6 ]1 T here are over 26 k indsof p lan ts of A can thop anax (D eche et P lanch1 )M iq1 in Ch ina including A . g racilisty lus, w h ichhas been listed in the Ch ina P ha rm acop oeia as Cor2tex A can thop anacis (nam ed as W u jiap i) [7 ] 1 Som elignan s and diterpene derivat ives from the roo t and
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Ξ 收稿日期: 20032082123 通讯作者
stem bark of A . g racilisty lus have been iso la ted
and iden t if ied [8 ]1 Fo r the pu rpo se of develop ing and
u t ilizing A can thop anax species resou rce grow ing in
A sia, the chem ical con st ituen ts of A . g racilisty lus
co llected in Changsha, H unan P rovince of Ch ina
have been system ically invest iga ted1 A s a resu lt,
eigh t lupane2t riterpeno ids including th ree new
compounds w ere ob ta ined from its ho t M eOH ex2
t racts and seven compounds of essen t ia l o ils from
the leaves, fou r compounds from the M eOH ex2
t racts and ten compounds of essen t ia l o ils from the
stem bark in ou r p reviou s papers[9212 ] 1 In th is
m anu2scrip t, the iso la t ion and iden t if ica t ion of six
compounds ob ta ined from the roo t of A . g raci2
listy lus are repo rted, they are (- ) 2p im ara29 (11) ,
152dien2192o ic acid (É ) [13 ] , ( - ) 2kau r2162en2192
o ic acid (Ê ) [14 ] , d 2sesam in (Ë ) [15 ] , st igm astero l
(Ì ) [16 ] , Β2sito stero l (Í ) [17 ] , and eleu thero side B
( Î ) [13 ] , respect ively. Among them , compoundsÉ , Ì , and Í are ob ta ined fo r the first t im e from
th is p lan t1
2　Exper im en t
211 　 P lan t m ateria ls1 T he samp les of A . g ra2
cilisty lus w ere co llected in M arch 2001 in Chang2
sha, H unan P rovince of Ch ina, and iden t if ied by
P rof1 YOO K Chang2soo , Co llege of Pharm acy,
Kyung H ee U n iversity in Ko rea1 A voucher speci2
m en has been depo sited in the Pharm acogno sy L ab2
o rato ry, Co llege of Pharm acy, Kyung H ee U n iver2
sity in Ko rea1
212　Genera l1 M elt ing po in ts (unco rrected) w ere
m easu red on a Boet iu s m icrom elt ing po in t appara2
tu s1 Op tica l ro ta t ion s w ere determ ined on a JA S2
CO D IP - 1000KU Y po larim eter ( l = 015 ) 1 IR
spectra w ere ob ta ined w ith a H itach i 270- 30 type
spectropho tom eter, and NM R spectra w ere m ea2
su red in m athano l2d 4 on a JEOL - Α- 500 spec2
t rom eter and chem ical sh if ts w ere rela t ive to te2
t ram ethylsilane (TM S) 1 Co lum n ch rom atography
(CC) w as carried ou t on silica gel 230- 400 m esh
(M erck) , D ia ion H P220P (M itsub ish i Chem 1 Ind1
Co1, L td1, Japan ) , Ch rom ato rex OD S ( 30 - 50Λm , Fu ji Silysia Chem 1 Ind1 Co1 L td1, Japan) and
Sephadex L H - 20 (Pharm acia B io tech, Sw eden) 1
TL C w as perfo rm ed on p recoated silica gel 60 GF
254 (M erck) and R P218F 254S (M erck) p la tes1
213　Ex tract ion and iso la t ion1 T he pow der of a ir2
dried roo t bark s w ere ex tracted w ith ho t M eOH
tw o tim es, and then separa ted w ith ether, 2214 g
of dried ex tract w as ob ta ined1 F rom them , 10 g
ex tracts w as ch rom atographed on silica gel CC u s2
ing n2hexane2E tOA c ( 10 ∶ 1 → 2 ∶ 1) , and fou r
fract ion s (F r1 A , B , C, and D ) w ere ob ta ined1
F ract ion A w as ch rom atographed on silica gel CC
elu t ing w ith n2hexane2E tOA c ( 10 ∶ 1 → 5 ∶ 1) ,
compounds É (100 m g) and Ê (20 m g) w ere ob2
ta ined1 F ract ion B affo rded compound Ë (10 m g)
by recrysta liza t ion1 F ract ion C affo rded compoundÌ (15 m g) by recrysta liza t ion1 F ract ion D elu ted
w ith hexane2E tOA c (40∶1) on silica gel co lum n
affo rded compound Í (20 m g) and compound Î
(16 m g) 1
3　 Iden tif ica tion
Compound É [ ( - ) 2p im ara29 ( 11 ) , 152
dien2192o ic acid ]: C 20H 30O 2, amo rphou s pow der,
mp 135 ℃- 136 ℃, IR ΜKB rm ax (cm - 1) : 3 290 (OH ) ,
1 690 (C= O ) , 1 638 (C = C) , 1 460, 1 075, 9651
1H 2NM R (500 M H z, CD 3OD ) ∆: 1103 (3H , s, H 2
20) , 1107 (3H , s, H 217) , 1118 (3H , s, H 218) ,
4186 ( 1H , dd, J = 1013, and 114 H z, H 216a ) ,
4198 ( 1H , dd, J = 1715, and 113 H z, H 216b ) ,
5141 ( 1H , m , H 211) , and 5184 ( 1H , dd, J =
1715, and 1018 H z, H 215) 1 13C2NM R (125 M H z,
CD 3OD ) ∆: 43124 t (C21) , 20128 (C22) , 38170
(C23) , 45116 (C24) , 49109 (C25) , 21162 (C26) ,
29119 (C27) , 29196 (C28) , 151138 (C29) , 39165
(C210) , 117172 (C211) , 39157 (C212) , 35191 (C2
13) , 43130 (C214) , 151151 (C215) , 109173 (C2
16) , 22176 (C217) , 29124 (C218) , 181168 (C2
19) , 23110 (C220) 1
Compound Ê [ (- ) 2kau r2162en2192o ic acid ]:
C 20H 30O 2, needle crysta ls, mp 179 ℃- 180 ℃, IRΜKB rm ax (cm - 1 ) : 3 420 (OH ) , 1 690 (C = O ) , 1 655,
and 875 (C= C) 1 1H 2NM R (500 M H z, CD 3OD ) ∆:
0197 (3H , s, H 220) , 1118 (3H , s, H 218) , 2161
(1H , m , H 213) , 4172 (1H , b rs, H 217a) and 4178
(1H , b rs, H 217b) 1 13C2NM R (125 M H z, CD 3OD )∆: 42110 (C21) , 20137 (C22) , 39124 (C23) , 44168
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(C24) , 58129 (C25) , 23113 (C26) , 42159 (C27) ,
45145 (C28) , 56156 (C29) , 40181 (C210) , 19150
(C211) , 34126 (C212) , 45126 (C213) , 40184 (C2
14) , 50118 (C215) , 156177 (C216) , 103175 (C2
17) , 29156 (C218) , 181168 (C219) , 16139 (C2
20).
Compound Ë (d 2sesam in ) : C20H 18O 6, co lo r2
less p rism s, mp 123 ℃- 125 ℃, [ Α]D - 68°(c =
110 in CHC l3) , IR ΜKB rm ax (cm - 1) : 2 969, 2 942, 2 904
(arom a2t ic CH ) , 2 825 ( a liphat ic CH ) , 1 500,
1 444 (arom atic C = C ) , 1 195 (arom atic2C2O ) ,
927 (m ethyl2ene ox im e) 1 R f value w as in agree2
m en t w ith its au then t ic samp le1
Compound Ì (st igm astero l) : C 29H 48O , co lo r2
less needles, mp 168 ℃- 169 ℃1 1H 2NM R (500
M H z, in CD 3OD ) ∆: 0173 ( s, 3H , H 218) , 0188,
0193 (each, 3H , H 226, and 27) , 0197 ( s, 3H , H 2
29) , 1104 ( s, 3H , H 219) , 1184 ( s, 3H , H 221) ,
3134 (m , H 23) , 4195 (1H , m , H 223) , 5119 (1H ,
m , H 222 ) , 5134 ( 1H , d, J = 512 H z, H 26 ) 1
13C2NM R ( 125 M H z, in CD 3OD ) ∆: 142123,
138151, 130160, 122144, 72144, 57146, 57137,
52180, 51173, 41192, 41115, 41103, 38155,
37143, 35110, 32129, 30137, 30118, 29135,
25131, 24114, 21176, 21154, 20118, 19185,
19140, 19131, 12133, 121301
Compound Í (Β2sito stero l) : C 29H 50O , needle2
like crysta ls, mp 138 ℃- 140 ℃1 E I2M S ( rel1
in t1 % ) : 414 (100) [M ]+ , 396 (45) , 329 (27) ,
303 (30) , 255 (15) , 145 (20) , 107 (25) , 95 (20).
Compound Î ( eleu thero side B ) : C 17H 24O 9,
w h ite needle crysta ls, mp 189 ℃- 190 ℃1
1H 2NM R ( 500 M H z, in CD 3OD ) ∆: 312023178
( 6H , m , gluco se2H ) , 3185 ( 6H , b rs, 2 ×2
OCH 3) , 4120 (2H , dd, J = 113 H z, 516 H z, H 29) ,
6135, 6155 (each 1H , m , H 27, and H 28) , 6174
( 2H , s, H 22, and H 26) 1 13C2NM R (125 M H z, in
CD 3OD ) ∆: 13512 (C21) , 10514 (C22 and C26) ,
15413 (C23 and C25) , 13519 (C24) , 13010 (C27) ,
13113 (C28) , 6316 (C29) , g luco se2carbon: 10513
(C21′) , 7517 (C22′) , 7718 (C23′) , 7113 (C24′) ,
7814 (C25′) , 6216 (C26′) , 5710 (2OCH 3) 1
References:
[ 1 ]　D an B, A ndrew G1 M ateria M ed ica [M ]1 (Revised edition)
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[ 2 ]　Yi J M , Kim M S, Seo S W , et a l1 A can thop anax w en ticosus
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m ent of O rien tal D rugs in Ko rea2D evelopm ent of B ioactive
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Kyungwon P ress, 20001
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Seou l: Kyungwon M edia, 20011
[ 7 ]　Ch P (中国药典) [S ]1 20001
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[ 9 ]　L iu X Q , Chang S Y, Yook C S, et a l1 T he essen tial o ils of
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草药) , 2001, 32 (12) : 1074210751
[ 10 ]　L iu X Q , Chang S Y, Park S Y, et a l1 Studies on the cons2
t ituen ts of the stem bark s of A can thop anax g racilisty lus [J ]1
N at P rod S ci, 2002, 8 (1) : 232251
[ 11 ]　Yook C S, L iu X Q , Chang S Y, et a l1 L upane triterpene
glyco sides from the leaves of A can thop anax g racilisty lus [J ]1
Chem P harm B u ll, 2002, 50 (10) : 1383213851
[ 12 ]　L iu X Q , Chang S Y, Park S Y, et a l1 A new lupane triter2
pene glyco sides from the leaves of A can thop anax g racilisty lus
[J ]1 A rch P harm R es, 2002, 25 (6) : 83128361
[ 13 ]　Kim Y H , Chung B S1 P im aradiene diterpenes from A can2
thop anax koreanum [J ]1 J N a t P rod , 1988, 51 (6) : 10802
10831
[ 14 ]　Chung B S, Kim Y1 P hy tochem ica l Investig a tion of A can2
thop anax koreanum , P roc1 Inst1 S ym 1 on N ew D rug D evel2
opm en t f rom N atu ra l P rod ucts [C ]1 Seou l: N ational U niver2
sity P ress, 1989, 51
[ 15 ]　Chung B S, Kim Y H 1 Studies on the constituen ts of A can2
thop anax koreanum , Ko r [J ]1 J P harm acog n, 1986, 17 (1) :
622661
[ 16 ]　Charles J P1 T he A ld rich L ibrary of 13C 2N M R and 1H 2N M R
F TN M R S p ectra [M ]1 N ew Yo rk (U SA ) : Purdue U niversi2
ty P ress, 19931
[ 17 ]　J ia Z J , L iu X Q , L iu Z M 1 T riterpeno ids from S ang u isorba
a lp ina [J ]1 P hy tochem istry , 1993, 32 (1) : 15521591
保　护　环　境　　保　护　植　被
·252· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 3 期 2004 年 3 月