全 文 ：西北植物学报 2002, 22( 6): 1457— 1459
Acta Bot . Boreal .-Occident. Sin.
文章编号: 1000-4025( 2002) 06-1457-03
祁州漏芦中一个新的蜕皮甾酮
程捷恺 1 ,黄明画 1 ,张自义 1 ,程东亮 1* ,张国林 2
( 1兰州大学化学系 ,应用有机化学国家重点实验室 ,兰州 730000; 2中国科学院成都生物研究所 ,成都
610041)
摘　要: 从祁州漏芦中分离得到 4个已知植物蜕皮甾酮、 1个地榆皂甙Ⅰ 以及 1个新植物蜕
皮甾酮。 经光谱分析 ( IR, M S, 1 HNM R, 13CNM R, DEPT , 1 H, 1H-CO SY , HM BC) ,推定这个新
天然产物为 2β , 3β , 11α, 14α, 20β , 23-hexahydro xy-5-cholest-7-en-6-one。 命名为异漏芦酮。
关键词: 祁州漏芦 ;菊科 ;植物蜕皮甾酮 ;异漏芦酮
中图分类号: Q946. 88　　　文献标识码: A
A new ecdysterone from Rhaponticum uniflorum
CHENG Jie-kai
1 , HU ANG Ming-hua
1 , ZHANG Zi-yi
1 ,
CHENG Dong-liang
1*
, ZHANG Guo-lin
2
( 1 Department of Ch emist ry, National Key Laboratory of Applied Organic Chemis try, Lanzhou Universi-
ty, Lan zh ou 730000, China; 2 Ch eng du Ins titute of Biology, Chines e Academy of Sciences, Chengdu
610041, China)
Abstract: A new ecdy sterone ( 5) , along wi th four known phy toecdysteroids and Ziyu
g lycoside I, w as isola ted f rom the roots of Rhaponticum unif lorum , which w as identified
as 2β , 3β , 11α, 14α, 20β , 23-hexahydroxy-5-cholest-7-en-6-one, designated as unif lors-
terone, by interpretation of the spect roscopic data ( IR, M S, 1HNM R, 13 CNM R,
DEPT,
1
H,
1
H-COSY, HMBC).
Key words: Rhaponticum uni f lorum; Composi tae; phy to ecdy steroids; unif loristerone
Rhaponticum unif lorum is dist ributed in nor thern China. It s ro ots has been used as a
收稿日期: 2002-01-23;修改稿收到日期: 2002-04-08
基金项目:国家自然科学基金资助项目 ( 2972010)
作者简介:程捷恺 ( 1967- ) ,男 (汉族 ) ,博士。
* 通讯联系人。 Co rrespond ence to: CHENG Dong-liang.
Chinese tradi tional medicine fo r the t rea tment of fev er and into xication
[1 ]
and i ts ethy l
acetate ex tract inhibits perox ida tion of membrane lipids and possesses an-
tiatherosclero tic activ ity. Recently , i ts chemical constituents including phy to ecdy steroids
have so far been repo rted. In a previous paper, w e have reported a new eudesmane
sesqui terpene, 7α, 8α, 12-trihydroxy-eudesma-4( 15) -11( 13) -diene, named rhaponticol ,
tog ether wi th thiophene deriva tiv es isolated f rom the pet roleum ether ex tract o f the
roots of R. uni f lorum
[2 ]
. During the course o f these studies, a new ecdysteroid, 2β , 3β ,
11α, 14α, 20β , 23-hexahydro xy-5-cholest-7-en-6-one, designa ted as unif loristerone ( 5) a-
long wi th daucto ro l ( 1) , ecdysterone ( 2) , ajug asterone C ( 3) , turkesterone ( 4) and ziyu
g lycoside I ( 6) have been isolated f rom the butanolic ex t ract of this plant.
Fig. 1　 Structur e o f uniflo risterone and some impo r tant HMBC co rr elations
Compound 5, colo rless prism, mp. 219℃～ 221℃ ( MeOH). It s molecular fo rmula C27
H44O7 was established by FABM S ( [M+ 1]+ a tm /z 481) and elemental analysis ( Found
C: 67. 39, H: 9. 32; Calcd. C: 67. 50; H: 9. 17) . Its IR spect rum show ed the presence o f hy-
droxyl ( 3 340 cm
- 1
and 3 409 cm
- 1 ) andα,β -unsa turated ketone ( 1 645 cm- 1 and 1 660
cm
- 1
) . The　 1 H NMR spectrum of 5 was quite simi lar to that o f 3[3 ] . Complete assign-
ment of the　 1 H and　 13 C NMR chemical shif t s w as achiev ed on the basis o f　 1H, 1 H-
CO SY and HMBC [4, 5 ] . The FABM S of 5 rev eals the prominent ions at m /z 481 [M+ 1 ]+
( 93) , 463 [M+ 1-H2O ]
+ ( 70) , 445 [M+ 1-2H2O ]
+ ( 40) , and fur ther f ragments were ob-
serv ed a t 427[ M+ 1-3H2O ]
+
( 26) , 423 [M-C4 H9 ]
+
( 12) , 393 [M-C5 H11O ]
+
( 31) , 379 [M -
C6 H13 O ]+ ( 20) , 361, 343, 338, 145, 127, 109, 101, 87 and 69 in EIM S. The peak a t m /z
145 corresponded to a side-chain ion a rising f rom cleavage between C-17 and C-20. Addi-
tional peaks at m /z 127 and 109 w ere o rig ina ted f rom them /z 145, due to lo ss o f one and
tw o molecules of w ater respectiv ely. The presence of one hydroxyl g roup a t C-23 in the
1458 西　北　植　物　学　报 22卷
side-chain was confo rmed from the fo rmation o f [ C5H11 O ]
+
and [C5H11 O-H2O ]
+
ion
peaks at m /z 87 and 69, respectiv ely, ascribed as the f ragmentation between C-22 and C-
23. On compa rison o f the EIM S fragmenta tion pat tern wi th those of 3, compound 5 may
be an isomer of 3, possessing same steroid nucleus, and the dif ference between 5 and 3
was only in the side chain. Th e side chain of 5 was determined by ana lysis of the HMBC
spect rum. Co rrela tion w ere found betw een H-23 and C-22, C-24; H-22 and C-20, C-23;
H-24 and C-23, C-25. Mo reover, w e found the co rrelation betw een H-17 and the signal of
methyl atδ18. 67, hence, this methyl should be assignment fo r C-19. Thus, the structure
o f 5 was elucidated as 2β , 3β , 11α, 14α, 20β , 23-hexahydroxy-5β-cholest-7-en-6-one, a new
ecdysteroid lacking a C-22 hydroxyl g roup [Fig. 1 ].
Acknowledgement: This w ork was suppo r ted by National Science Foundation o f China ( No:
2972010) and w as a lso suppo r ted by the Na tional Key Labor ato ry of Applied O rganic Chemistry of
Lanzhou Univ er sity o f China.
Ref erence:
[1 ]　 NEW M EDICAL CO LLEGE OF JIANGSU. The encyclopedia of t radi ti onal chines e m edicine [M ] . Shanghai:
Shanghai Science and Technology Pres s, 1985: 2 348.
[2 ]　 WEI HX, GAO W Y,W EIW Y, et al . New eud esmane sesqui terpen e and thioph ene deriv atives f rom the root s of
Rhapont icum uni f lorum [ J] . Pharmazie, 1997, 52: 245.
[3 ]　 ZHAN G M, STIU T M J, KU BG I. Isolation of ecd ys teroids f rom V itex str ickeri using RLCC and recycling HPLC
[ J] . Phytoch emis t ry, 1992, 31( 1): 247.
[4 ]　 1H-NM R data of unif lo ris terone 5( CD3OD,δppm J, Hz ): 1. 36 [1H, t , ( 12. 8) , H-1a ] , 2. 57[ 1H,dd , ( 4. 0, 12. 8) ,
H-1b ] , 3. 98 [1H,d t , ( 4. 0, 12. 8) , H-2] , 3. 95 [1H, m , H-3 ] , 1. 72 [1H,m , H-4a ] , 1. 77 [1H, m , H-4b ] , 2. 19 [1H,
dd , ( 4. 0, 9. 5) , H-5 ] , 5. 79 [1H,d , ( 2. 0) , H-7 ] , 3. 13 [1H,dd , ( 2. 0, 6. 8) , H-9 ] , 4. 09 [1H,m , H-11 ] , 2. 20 [1H,
m , H-12a ] , 2. 15 [1H,m , H-12b ] , 1. 94 [1H,m , H-15a ] , 1. 58 [1H,m , H-15b ] , 1. 97[ 1H, m , H-16a] , 1. 75 [1H,m ,
H-16b ] , 2. 41 [1H,m , H-17 ] , 1. 04 [3H, s , H-18 ] , 0. 86 [3H, s, H-19] , 1. 20 [3H, s , H-21 ] , 1. 45 [1H,dd , ( 9. 2, 2.
0) , H-22a] , 1. 33 [1H,m , H-22b ] , 3. 30 [1H,brs , H-23 ] , 1. 55[ 2H,m , H-24 ] , 1. 57 [ 1H, m , H-25 ] , 0. 90 [3H,m , H-
26 ] , 0. 91 [3H,m , H-27 ].
[ 5 ]　 13CNM R( CD3OD,δppm) of uni f lori s terone 5: 39. 97( C-1) , 68. 43( C-2) , 68. 8( C-3) , 33. 17 ( C-4) , 52. 66 ( C-5) ,
206. 64( C-6) , 122. 67( C-7) , 165. 65 ( C-8 ) , 42. 82 ( C-9 ) , 39. 83 ( C-10 ) , 69. 42 ( C-11) , 43. 67 ( C-12) , 48. 36 ( C-
13 ) , 84. 85 ( C-14) , 31. 76( C-15) , 21. 44( C-16) , 50. 13( C-17) , 24. 58( C-18) , 18. 67 ( C-19) , 77. 76( C-20) 20. 95
( C-21) , 37. 56( C-22) , 77. 86( C-23) 30. 38( C-24) , 29. 14( C-25) , 22. 72 ( C-26) , 23. 41( C-27) .
14596期 程捷恺等: 祁州漏芦中一个新的蜕皮甾酮 (英 )