全 文 ：C= O )、5 个CH、2 个CH 2 及 4 个CH 3。上述数据与 文献[6 ]报道金丝梅酮基本一致。
表 3　化合物Ì 的 NM R 谱数据[ in (CDCl3) 2CO , 500 M Hz for ∆H, 125 M Hz for ∆C ]
Table 3　NM R data of compound Ì [ in (CDCl3) 2CO , 500 M Hz for ∆H, 125 M Hz for ∆C ]
C 位 13C2NM R 1H 2NM R C 位 13C2NM R 1H 2NM R C 位 13C2NM R 1H 2NM R
1 　56157 　 7 100113 6123 (1H , d, J = 118 H z) 10a 157172
2 201103 8 161102 13118 (1H , s, 82OH ) 1′×2 38132 3142 (2H , dd, J = 1315, 714 H z)
2171 (2H , dd, J = 315, 714 H z)
3 164154 9127 (1H , br, 32OH ) 9 179183 2′×2 117102 4172 (2H , t, J = 714 H z)
4 109105 6163 (1H , s, 42OH ) 8a 104192 3′×2 135114
5 94106 6135 (1H , d, J = 118 H z) 9a 116133 4′×2 25143 1145 (6H , s)
6 163162 4a 154188 5′×2 18105 1145 (6H , s)
　　化合物Í : 无色粒晶, mp 234 ℃～ 237 ℃ (氯
仿2丙酮)。E IM S m öz (% ) : 258 (M + , 20) , 243 (M -
15, 100) , 215 (M - 28, 18)。IR 中3 300, 1 670, 1 640
cm
- 1处有强吸收带。UV 中在 230, 260, 330, 405 nm
处有吸收带, 与化合物 Ì 类似, 为　酮结构。
1H 2NM R谱证明, 有 2 个酚羟基 (∆12111, 10120) , 还
有 5 个芳烃质子 (∆7175, 7166, 7158, 7150, 7140) 和
1 个甲氧基 (∆3144)。上述数据与文献[7 ]报道一致,
故指认化合物Í 为 1, 72二羟基242甲氧基　酮。
化合物Î : 淡黄色粒晶,mp 196 ℃～ 198 ℃ (氯
仿2丙酮)。E IM S m öz (% ) : 328 (M + , 40) , 313 (M -
15, 25) , 285 (M - 15- 28, 100) , 272 (25) , 164 (20)。
由 UV 中 247, 260, 320, 370 nm 处的吸收带及
1H 2NM R [ ∆13151 (酚羟基) , ∆6182, 6128, 6121 (3 个
芳烃质子) , ∆5130 ( t, J = 518 H z, = CH ) , 4118 (d,
J = 611 H z, = CH ) ], 可推测化合物为带侧烯链的　
酮成分。上述数据与文献[8 ]对照一致, 指认化合物Î
为 1, 3, 6, 72四羟基282(32甲基2丁222烯基) 酮。 References:[ 1 ]　 Institu tum Batan icum Kunm inggense A cadem iae Sin icae Edi2ta1 Ind ex F lorae Y unnanensis (云南种子植物名录) [M ]1(Tom us É ). Kunm ing: Yunnan Peop le’s Pub lish ing House,19841[ 2 ]　L i H H , Ken Y S1 Comp lex caged po lyisop renylated ben2zophenone derivatives, samp son iones A and B from H yp er2icum samp son ii [J ]1 T etrahed ron L ett, 1988, 39: 7999280021[ 3 ]　L i H H , Ken Y S1 Samp son iones C- H , a un ique fam ily ofpo lyp renylated benzophenone derivativesw ith the novel tetra2cyco l [ 7131111103, 7 ] tetradecane22, 12, 142trione skeleton,from H yp ericum samp son ii [J ]1 T etrahed ron L ett, 1999, 40:75927621[ 4 ]　L i H H , Ken Y S1 Samp son iones A - M , a un ique fam ily ofcaged po lyp renylated benzoylph lo roglucino l derivatives fromH yp ericum samp son ii [J ]1 T etrahed ron, 2000, 56 ( 12 ) :1379213861[ 5 ]　W ang Y, W ang S S, Zhou D H , et a l1 Spectral characteris2t ics of phytoxan thones [J ]1 N at P rod R es D ev (天然产物研究与开发) , 2002, 14 (5) : 852901[ 6 ]　Cardona M L , Fernandez I, Pedro J R 1 Xanthone cons2t ituen ts of H yp ericum inod orum [J ]1 H eterocy cles, 1992, 34(3) : 47924821[ 7 ]　N ielsen H , A rends P1 Xanthone constituen ts of H yp ericumand rosaem um [J ]1 J N a t P rod , 1979, 42 (3) : 30123041[ 8 ]　 Ish iguro K, N akajim a M , Su itan i A , et a l1 A p renylatedxan thone from cell suspension cu ltu res of H yp ericum p a tu2lum [J ]1 P hy tochem istry , 1997, 44 (6) : 1065210661
Stud ies on chem ica l con stituen ts of Cyp r ip ed ium sm ith ii
JU J ian2hua, ZOU Zhong2jie3 , YAN G Jun2shanΞ
( Inst itu te of M edicinal P lan t D evelopm ent, Ch inese A cadem y of M edical Science
and Pek ing U nion M edical Co llege, Beijing 100094, Ch ina)
　　Abstract: Object　To study the chem ical con st ituen ts of Cyp rip ed ium sm ith ii L 1 M ethods　Com 2
pounds w ere iso la ted by repeated silica gel ch rom atograph ies and their st ructu res w ere determ ined by spec2
t ra l analysis1 Results　F ive compounds w ere iso la ted from C 1 sm ith ii and their st ructu res w ere iden t if ied
as Β2sito stero l (É ) , 42hydroxybenzyl m ethyl ether (Ê ) , 42hydroxybenzyl ethyl ether (Ë ) , ba ta tasin É
62hydroxy22, 4, 72t rim ethoxyphenan th rene (Ì ) , bis [ 42(Β2D 2glucopyrano syloxy) 2benzyl ] (s) 2(2) 222sec2
bu tylm ala te (Í ) 1 Conclusion　A ll compounds are ob ta ined from th is p lan t fo r the first t im e1
Key words: Cyp rip ed ium sm ith ii L. ; chem ical con st ituen ts; Cyp rip ed ium L.
·431· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 2 期 2004 年 2 月
Ξ 收稿日期: 2003204222
作者简介: 鞠建华, 男, 副研究员, 主要从事天然药物化学方面的研究。
褐花杓兰化学成分的研究
鞠建华, 邹忠杰3 , 杨峻山3
(中国医学科学院 中国协和医科大学药用植物研究所, 北京　100094)
摘　要: 目的　研究褐花杓兰Cyp rip ed ium sm ith ii 的化学成分。方法　反复硅胶柱色谱进行分离, 并通过波谱分析
方法鉴定化合物结构。结果　分离并鉴定了 5 个化合物, 分别为: Β2谷甾醇 (Β2sito stero l, É ) , 对羟基苄基甲基醚 (42
hydroxybenzyl m ethyl ether, Ê ) , 对羟基苄基乙基醚 (42hydroxybenzyl ethyl ether, Ë ) , 山药素É (bata tasin É , 62
hydroxy22, 4, 72t rim ethoxyphenan th rene, Ì ) , 二[42(Β2D 2吡喃葡萄糖氧)苄基 ] (s) 2(2) 222仲丁基苹果酸酯 (Í )。结
论　所有化合物均为首次从本植物中分得。
关键词: 褐花杓兰; 化学成分; 杓兰属
中图分类号: R 28411　　　文献标识码: A 　　　文章编号: 0253 2670 (2004) 02 0134 03
　　P lan ts of Cyp rip ed ium L 1 mo st ly po ssess the
funct ion of d iu resis, detum escence, sedat ion, anal2
gesia, et a l [1 ] 1 In ou r studies on chem ical con s2
t ituen ts of C 1 sm ith ii, f ive compounds w ere iso la t2
ed by ch rom atograph ies and their st ructu res w ere
iden t if ied as Β2sito stero l ( É ) , 42hydroxybenzyl
m ethyl ether ( Ê ) , 42hydroxybenzyl ethyl ether
( Ë ) , ba ta tasin É ( 62hydroxy22, 4, 72t rim e2
thoxyphenan th rene ( Ì ) , bis [ 42( Β2D 2glucopyra2
no syloxy) 2benzyl ] (s) 2(2) 222sec2bu tylm ala te (Í ) 1
1　Appara tus and ma ter ia ls
M elt ing po in ts of the compounds w ere deter2
m ined w ith a F isher2John s appara tu s1 IR spectra
w ere reco rded w ith a Perk in2E lm er 983 G spec2
t rom eter1 NM R spectra ( 500 M H z fo r 1H 2NM R
and 125 M H z fo r 13C2NM R ) w ere m easu red w ith a
Bu rker AM - 500 spectrom eter, u sing TM S as in2
ternal standard1 Coup ling con stan ts (J values )
w ere given in H z1 A V G ZAB - 2F m ass spectrom 2
eter w as u sed to reco rd the E I2M S, and an A u2
to spec2U lt im a ETO F spectrom eter w as u sed to
reco rd the FAB 2M S1 Silica gel and silica gel GF
254 sheets (0120- 0125 mm ) (bo th from Q ingdao
M arine Chem ical Group Co1, Q ingdao , Shandong
P rovince, Ch ina) w ere u sed fo r co lum n ch rom ato2
graphy and TL C, respect ively1 Sephadex L H 220
(Pharm acia, 40 Λm ) w as pu rchased from Sigm a
Chem icals1
2　Extraction and isola tion
T he dried p lan t m ateria l (5 kg) w as ex tracted
w ith ethano l under reflux th ree t im es ( 550 g ) 1
Su spended in w ater, it w as ex tracted w ith
spect ively1 T he petro leum ether2so lub le fract ion
( 6510 g ) w as iso la ted by repeated co lum n ch ro2
m atograph ies w ith silica gel 60H to affo rd com 2
pounds É (200 m g) , Ê (30 m g) , Ë (50 m g) 1
T he ethyl aceta te residue (4210 g) w as sub jected
to co lum n ch rom atography on silica gel 60 H
(400- 500 m eshes) w ith a CHC l32M eOH gradien t
system repeated ly and pu rif ied on Sephadex L H 220
w ith CHC l32M eOH (1∶1) to affo rd compounds Ì
(35 m g) , Í (40 m g) 1
3　 Iden tif ica tion
Compound É : Co lo rless needles, mp
137 ℃- 139 ℃; IR ΜKB rm ax cm - 1: 3 420 (OH ) , 2 980,
2 960, 1 650 (C = C ) ; E I2M S m öz 414 [M + ]
( 65) , 396 (68) , 381 (37) , 329 (35) , 303 (40) ,
273 ( 31) , 255 ( 65) , 233 ( 30) , 213 ( 55) , 159
(55) , 81 (100) 1 It w as iden t if ied as Β2sito stero l by
spectra l analysis and comparison w ith an reference
samp le1
Compound Ê : Co lo rless p rism s, mp 80 ℃-
82 ℃; 1H 2NM R (DM SO 2d6 ) ∆: 9141 ( 1H , b rs,
OH ) , 7110 and 6175 (each 2H , d, J = 815 H z, H 2
2, 6, 3, 5) , 4125 (2H , s, H 27) , 3121 (3h, s,
OCH 3) ; 13C2NM R (DM SO 2d6 ) ∆: 15710 (C24) ,
12914 (C22, 6) , 12815 (C21) , 11510 (C23, 5) ,
7316 (C27) , 5710 (OCH 3) 1 It w as iden t if ied as 42
hydroxybenzyl m ethyl ether by spectra l analysis
and comparison w ith data of litera tu re [2 ]1
Compound Ë : Co lo rless needles, mp 50 ℃-
52 ℃; 1H 2NM R (DM SO 2d6 ) ∆: 9133 ( 1H , b rs,
OH ) , 7110 and 6173 (each 2H , d, J = 815 H z, H 2
2, 6, 3, 5) , 4129 (2H , s, H 27) , 3140 (2H , q, J =
′) ( 0 H z, H 22′) ;
·531·中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 2 期 2004 年 2 月
13C2NM R (DM SO 2d6) ∆: 15618 (C24) , 12912 (C2
2, 6) , 12818 (C21) , 11419 (C23, 5) , 7116 (C27) ,
6415 (C21′) , 1511 (C22′) 1 It w as iden t if ied as 42
hydroxybenzyl ether by spectra l analysis and com 2
parison w ith data of litera tu re [3 ]1
Compound Ì : B row n amo rphou s pow der,
FAB 2M S; 30710 [M + N a ]+ , 28410 [M ]+ ;
1H 2NM R (DM SO 2d6) ∆: 9137 (s, OH ) , 8199 (1H ,
s, H 25) , 7159 and 7153 (each 1H , d, J = 910 H z,
H 29, 10) , 7123 ( 1H , s, H 28) , 7100 and 6180
(each 1H , d, J = 215 H z, H 21, 3) , 4107, 3195,
3188 (each 3H , s, OCH 3) ; 13C2NM R (DM SO 2d6)∆: 15816 (C22) , 15619 (C24) , 14719 (C27) , 14513
(C26) , 13319 (C210a) , 12710 (C24b) , 12619 (C2
8a ) , 12417 (C29) , 12316 (C210) , 11418 (C24a) ,
11119 (C25) , 10818 (C21) , 10115 (C28) , 9910
(C23) , 5519, 5512, 5511 (OCH 3) 1 It w as iden t i2
f ied as 62hydroxy22, 4, 72t rim ethoxyphenan th rene
by spectra l analysis and comparison w ith data of
litera tu re [4, 5 ]1
Compound Í : W h ite pow der; mp 108 ℃-
109 ℃; FAB 2M S: 74913 [M + N a ]+ , 76513 [M +
K ]+ ; 1H 2NM R (DM SO 2d6) ∆: m alic acid mo iety:
2183 and 2160 (each 1H , d, J = 1515 H z, H 23) ,
1154 (1H , m , H 25) , 0196 and 1122 (each 1H , m ,
H 26) , 0174 (3H , t, J = 715 H z, H 27) , 0180 (3H ,
d, J = 7 H z, H 28) , benzyl mo iety: 7100 and 7125
(each 4H , d, J = 815 H z, H 22′, 6′, 2″, 6″, 3′, 5′,
3″, 5″) , 5102 (2H , s, H 27′) , 4192 (2H , s, H 27″) ,
g luco se mo iety: 4183 (2H , d, J = 715 H z, H 21×2) ,
3112- 3132 (8H , m , H 22, 3, 4, 5×2) , 3166 and
3145 (each 2H , m , H 26) ; 13C2NM R (DM SO 2d6 )∆: m alic acid mo iety: 17410 (C21) , 7718 (C22) ,
4117 (C23) , 17010 (C24) , 4214 (C25) , 2314 (C2
6) , 1212 ( C27 ) , 1213 ( C28 ) , benzyl mo iety:
15712 (C21′, 1″) , 11611 (C22′, 6′, 2″, 6″) , 12916
(C23′, 5′, 3″, 5″) , 12911 (C24′, 4″) , 6518 (C2
7′) , 6513 (C27″) , g luco se mo iety: 10013 (C21×
2) , 7311 and 7312 (C22) , 7615 and 7610 (C23) ,
6916 and 6917 (C24) , 7710 (C25×2) , 6017 and
6015 (C26) 1 It w as iden t if ied as bis [ 42(Β2D 2glu2
copyrano syloxy) 2benzyl ] (s) 2(2) 222sec2bu tylm ala te
by spectra l analysis and comparison w ith data of
litera tu re [6 ]1
References:
[ 1 ]　W u Z Y1 Comp end ium of N ew Ch ina (X inhua) H erba l (新华
本草纲要) [M ]1 V o l 31 Shanghai: Shanghai Scien tific and
T echn ical Pub lishers, 19911
[ 2 ]　T aguch i H , Yo sioka I, Yam asak i K, et a l1 Studies on the
constituen ts of Gastrod ia ela ta B lum e [J ]1 Chem P harm
B u ll, 1981, 29 (1) : 552621
[ 3 ]　Zhou J , Pu X Y, Yang Y B1 N ine pheno lic componen ts from
fresh Gastrod ia ela ta [J ]1 Ch in S ci B u ll (科学通报) , 1981,
(18) : 1118211201
[ 4 ]　M ajum der P L , Banerjee S, Sen S1 T h ree stilbeno ids from
the o rch id A g rostop hy llum ca llosum [J ]1 P hy tochem istry ,
1996, 42 (3) : 84728521
[ 5 ]　Coxon D T , O gunadana S K, D enn is C1 A ntifungal phenan2
th renes in yam tubers [J ]1 P hy tochem istry , 1982, 21 ( 6) :
1389213921
[ 6 ]　L i Y M , Zhou Z L , Hong Y F1 Studies on the pheno lic cons2
t ituen ts of Galeola f aberic [J ]1 A cta P harm S in (药学学报) ,
1993, 28 (10) : 76627711
遍地金的化学成分研究
陶曙红, 吴凤锷Ξ
(中国科学院成都生物研究所 天然产物中心, 四川 成都　610041)
　 　 遍 地 金 H yp ericum w ig h tianum W all1 ex
W igh t et A rn. 属藤黄科金丝桃属植物, 全草入药。
分布于云南、四川、贵州、西藏等省。有收敛止血、清
热解毒的功效。民间用于治疗小儿炎症、久痢、久泻、
毒蛇咬伤等疾病[1 ]。近年来, 由于金丝桃属植物在抗
抑郁和抗病毒方面的突出作用[2～ 5 ], 该属植物的研
究受到普遍重视。我国金丝桃属植物有约 50 种, 多
为特有种, 但大部分未做化学成分研究或研究不深
入。遍地金的化学成分国内外尚未见报道, 为更好地
开发和利用我国金丝桃属植物资源, 我们对遍地金
·631· 中草药　Ch inese T radit ional and H erbal D rugs　第 35 卷第 2 期 2004 年 2 月
Ξ 收稿日期: 2003205210
作者简介: 陶曙红 (1974- ) , 女, 湖南安化人, 中国科学院成都生物研究所植物化学专业在读硕士研究生。　T el: (028) 85229073　
E2m ail: tsh106@etang1com