全 文 ：化合物Ⅷ :无色针晶 (石油醚 ) , mp 234℃～ 235
℃ , Liebermann-Burcha rd反应紫红色。1HNMRδ:
( CDCl3 ): 0. 80( 3H, s, CH3 ) , 0. 84( 6H, s, 2× CH3 ) ,
0. 85( 9H, s, 3× CH3 ) , 0. 94( 3H, s, CH3 ) , 1. 10( 3H,
s, CH3 )为 8个甲基。13 CNMR中有 32个碳峰 , 30～
42范围内有 6个季碳 ,提示该化合物为齐墩果烷五
环三萜化合物。 IR提示含有酯羰基 ( 1 738)。1H-
NMR 2. 03处有一酰甲基 ,碳谱中 171( s) , 21. 3( q)
峰的存在 ,说明化合物中含有 CH3 COO-基团 , IR谱
1 656 cm
- 1信号示有一双键 , 1 HNM R 5. 16( 1H, t )
示为环内双键 (因 δ> 5)。13 CNM R 145( s) , 121( d)
信号的存在 ,提示该化合物为△12 -齐墩果烯类衍生
物。根据以上分析为 β -香树脂醇乙酸酯。且 EI-M S
与文献值 [4 ]完全一致 ,故可确定为 β -香树脂醇乙酸
酯。
化合物Ⅸ : 白色针羽晶 , mp 210℃～ 211℃ ,
Liebermann-Burchard反应紫红色。 IR( KBr ) cm- 1:
1 735( -COOR) , 1 240, 1 638( C= C)。EI-M S( m /z):
468 ( M+ ) , 453 ( M - CH3 ) , 249, 218, 203,
189。1 HNMRδ: ( CDCl3 ): 4. 66( 1H, br, H-30) , 4. 54
( 1H, br, H-30) , 4. 45 ( 1H, m, H-3) , 2. 03 ( 3H, s,
Ac) , 1. 66( 3H, s, CH3-29) , 1. 00( 3H, s, CH3 ) , 0. 91
( 3H, s, CH3 ) , 0. 83( 3H, s, CH3 ) , 0. 82( 3H, s, CH3 ) ,
0. 81( 3H, s, CH3 ) , 0. 76( 3H, s, CH3 )。13 CNMR与羽
扇豆醇乙酯的文献值 [ 9]完全一致 ,故可确定为羽扇
豆醇乙酯。
致谢:元素分析由中科院成都分院有机所代测 ,
其它光谱数据由华西医科大学药学院中心测试室代
测。
参 考 文 献
1　中科院西北高原生物所编著 .藏药志 . 西宁:青海人民出版社 ,
1991: 99
2　青海省藏医药研究所 ,等主编 . 中国藏药 . Vol. 3,上海: 科学技
术出版社 , 1997: 103
3　于德泉 ,等 .分析化学手册 V.核磁共振波谱分析 .北京:化学
工业出版社 , 1989: 48, 823
4　丛浦珠 . 质谱学在天然有机化学中的应用 . 北京: 科学出版社 ,
1981: 754, 689, 692
5　 Rubins teinⅠ , et al . Phytoch emis t ry, 1976, 15: 195
6　王建忠 ,等 .天然产物研究与开发 , 1996, 8(2) : 8
7　陈业高 ,等 .中国中药杂志 , 1995, 20( 10): 610
8　 Bud zikiew ice H, et al . J Am Chem Soc, 1963; 85, 3697
9　 Sh olichin M , et al . Chem Ph arm Bul l, 1980, 28(3) : 1006
( 1999-02-03收稿 )
Minor Phenolic Constituents of Chinaberry-tree (Melia azedarach)
Depar tment of Ph yto chemistry , China Pha rmaceutical Unive rsity ( Nanjing 210009)　 Li Shish eng , Deng Jing zhen and
Zhao Shouxun
Abstract　　 Five mino r ferulic acid esters (Ⅰ ～ Ⅴ ) w ere identified in a pet ro l ex t ract of Melia
azedarach stem bark, one (Ⅰ ) of w hich w as isolated w ith no impuri ty fo r th e fi rst time. By chemical and
spect ral methods, thei r st ructures w ere elucidated as hexacosy lferulate (Ⅰ ) ; tet racosylferulate (Ⅱ ) ;
pentaco sylferula te (Ⅲ ) ; heptacosylferula te (Ⅳ ) a nd octacosylferulate (Ⅴ ) , respectively.
Key words　　 Melia azedarach L. 　 hexaco syl ferulate　 tet racosylferulate　 pentaco sy lferulate　
heptaco syl ferulate　 octaco sylferula te
摘　要　从苦楝茎皮中提取分离并鉴定了 5个微量酚性化合物。 它们的结构分别为阿魏酸二十六醇酯 (Ⅰ )、
阿魏酸二十四醇酯 (Ⅱ )、阿魏酸二十五醇酯 (Ⅲ )、阿魏酸二十七醇酯 (Ⅳ )、阿魏酸二十八醇酯 (Ⅴ )。均为从苦
楝中首次分离得到。
关键词　苦楝　阿魏酸二十六醇酯 (Ⅰ )　阿魏酸二十四醇酯 (Ⅱ )　阿魏酸二十五醇酯 (Ⅲ )　阿魏酸二十七
醇酯 (Ⅳ )　阿魏酸二十八醇酯 (Ⅴ )
Introduction
Melia azedarach L ( Meliaceas ) i s widely
dist ributed in Asia, Africa and o ther t ropical
regions o f the w o rld. Di fferent pa rts of the tree
have long been used as a t radi tional fo lk medicine
fo r the t reatment of a va riety of human ai lments
·86· 中草药　 Ch inese Tradi tional and Herbal Drugs　 2000年第 31卷第 2期
李石生 ,中国药科大学天然药物化学教研室 (南京 210009)
such as rheumatism, leprosy, scrofula , i tch and
eruptiv e skin disease
[1 ] . Among o thers, antivi ral,
antihelminthic, emmenagog ic and anti tumo r
activi ties have also been reported
[2 ]
. In o rder to
exploi t i ts potential use as an antineoplastic ag ent ,
systema tic chemical and pharmacological actions of
the stem ba rk of M. azedarach L. have been
studied by our g roup. Ex tensiv e investig ation on a
pet ro l ex t ract of the stem bark has resulted in the
isolation of hexaco sy lferulate ( Ⅰ ) w ith no
impuri ty for the fi rst time and the determina tion of
four o ther mino r (Ⅱ ～ Ⅴ ) long chain fat ty alcohol
esters o f ferulic acid. The chemical st ructures of
(Ⅰ ～ Ⅴ ) w ere show n in Fig 1.
Fig. 1　 The chemical sructures of compoundsⅠ ～ Ⅴ
Results and Discussion
The petrol-so luble f raction o f the stem ba rk of
M. azedarach L. w as separated by repeated open
column chroma tog rah py and recrystalli za tion ( see
experimental ) to giv e a mino r ferulic acid ester,
hexacosy lferulate (Ⅰ ) , which was isolated in a
pure sta te fo r the fi rst time, and a mix t o f four
o ther mino r ferulic acid esters (Ⅱ～ Ⅴ ) .
Hexacosylferulate (Ⅰ ) was crystalli zed f rom
petro l-EtO Ac ( 8. 5 ∶ 1. 5 ) as needles. It s
molecular formula w as determined a s C36 H62O4 by
HRF-AB-M S, and i ts IR spect rum , in addi tion to
i ts po sitiv e results wi th FeCl3 reagents and
negativ e results wi th Emerson reagents, indicated
that i t was a ferulic acid ester
[3 ]
. This conclusion
w as confirmed by the observ ation o f NO E 5. 8%
fo r signalδ7. 04 when signalδ3. 93 w as i rradiated.
The
1
HNMR spectral data w ere simila r to those of
hexacosy lacetox yferulate except an acetox y peak at
δ2. 30 was missing and an addi tional peak appeared
a tδ5. 87 ( disappea red when D2O was added) a s
broad singlet for hydro xy g roup
[4 ] . These results
are consistent wi th formula I as show n.
Hexacosy lferulate was isola ted in the pure state fo r
the first time. Assignments of the
1
H and
13
CNMR
signals w ere show n in Table 1.
The mix esters Ⅱ ～ Ⅴ was composed of
homologues of hexacosy lferulate deducing f rom i ts
simila r spect ral data ( IR;
1
H,
13
CNM R) to those
of compound Ⅰ . FAB-M S indica ted the presence
of tetraco sy lferulate ( Ⅱ ) , pentacosylferulate
(Ⅲ ) , heptacoslferulate (Ⅳ ) and octacosylferulate
(Ⅴ ) , HRFAB-M S confi rmed their mo lecula r
fo rmula as C34 H58O4 , C35 H60O4 , C37 H64O4 and C38
H66O4 respectiv ely ( see Table 2) . Reversed phase
chromato gram of the mix t rev ealed the ex istence of
four homo logues ( see experimental ) . The mix t of
compounds Ⅱ ～ Ⅳ had been identi fied in
Spiranthes sinensis ( Pers. ) Ames var. amoean ( M.
Bieberson ) Ha ra[ 5] . Octacosylferula te (Ⅴ ) had
also been iso la ted f rom Tecomel la undulata ( G.
Don) Seem and Gmelina arborea Roxb
[6, 7 ] .
Table 1.　 1H and 13CNMR Data of Compounds
Ⅰ ～ Ⅴ (CDCl3 )
posit ion 13Cδ DEPT 1Hδ　 JH, H ( Hz)
1 127. 0 C 　 - -
2 109. 2 CH 7. 04( d) 1. 5
3 147. 9 C 　 - -
4 146. 7 C 　 - -
5 114. 7 CH 6. 92( d) 8. 0
6 123. 0 CH 7. 07( dd) 1. 5; 8. 0
7 144. 6 CH 7. 61( d) 16. 0
8 115. 7 CH 6. 30( d) 16. 0
9 167. 4 C= 0 　 - -
MeO 55. 9 CH3 3. 93( s) -
HO - - 5. 87( br. s ) -
1’ 64. 6 CH2 4. 19( t ) 6. 7; 6. 7
2’ 31. 9 CH2 1. 69( m) -
3’ 26. 0 CH2 1. 64( m) -
4’ to ( n-3) 28. 8～ 129. 7 CH2 1. 25( m) -
( n-2) 31. 9 CH2 1. 25( m) -
( n-1) 22. 7 CH2 1. 25( m) -
Me 14. 1 CH3 0. 88( t ) 6. 6; 6. 6
　 　 It was repor ted tha t pharmaceuticals
containing alky l ferula tes had been used fo r the
t rea tment of alcoholism
[8, 9 ] . Ferulic acid and a few
ferulic acid esters had been repor ted to possess
allelopa thic effects
[10, 11 ]
. The isolation and
determina tion of minor ferulic acid esters wi th long
chain fa t ty alcoho ls occurring in lipid-soluble
ex tract o f M. azedarach L. is of interest , although
·87·中草药　 Ch inese Tradi tional and Herbal Drugs　 2000年第 31卷第 2期
the biological significance is not yet clear and
remains to be studied fur ther.
Experimental
General　 Mps: unco rr. ; IR: KBr; NMR:
1
H, a t 300 M Hz,
13
C( DEPT) at 75 M Hz, CDCl3 ;
FAB-M S and HRFAB-M S: negative ion mode;
HPLC: Va rian HPLC system , ODS colunm ,
mobile phase: MeOH-H2O-isopropyl alcohol-
HO Ac ( 78∶ 20∶ 1. 5∶ 0. 5) , UV: λ254 nm , f low
ra te : 1. 0 mL /min.
Plant material 　 M. azedarach L. wa s
collected f rom Jishui county, Jiangx i prov ince,
China in Aug. , 1995. The species wa s
authenticated by Dr. J. Z. Deng , China
Pha rmaceutical Univ ersity, where a vouched
specimen has been deposi ted.
Ex t raction and sepa ra tion　 The air-dried
powdered stem bark ( 20 kg ) was continuously
ex t racted w ith refluxing 95% EtO H and the
ex t racts concd. in vacuo. The residue was
suspended in H2O and the mix t, was successiv ely
ex t racted wi th pet rol , EtO Ac and n -BuOH. The
combined petrol layers w ere concd. to dryness to
giv e a pet rol f r. ( 200 g ) , which w as subjected to
CC ( silica gel ) , eluting wi th pet rol-EtO Ac mix ts
o f increasing po lari ty. Frs. w ere moni to red by
T LC. Fr. 83 ( 15 mg ) ( pet rol-EtO Ac 92∶ 8)
show ed posi tiv e resul ts w ith FeCl3 reagents. Af ter
repea ted si lica gel CC and recrystallization several
times in petro l-EtO Ac ( 8. 5∶ 1. 5) , compoundⅠ
( 5 mg) as needles and the mix t (Ⅱ ～ Ⅴ ) as w hi te
pow der ( 4 mg ) w ere iso lated f rom fr. 83.
Hexacosylferulate Ⅰ 　 Needles; posi tive
resul ts wi th FeCl3 reagents, nega tiv e results wi th
Emerson reagents; mp 69℃～ 70. 5℃ ; HRFAB-
M S ( neg. ) m /z: 557. 459 0 ( calcd 557. 457 0 fo r
C36 H61O4 ) ; FAB-M S ( neg. ) m /z: 557 ( [M- 1 ]
- ,
100) , 193 ( [M - hexaco sanyl ]
- , 31) , 175 ( 21) ,
161 ( 20) , 148 ( 23) , 133 ( 27) ; IRνKBrmax cm- 1: 3 410,
2 910, 2 850, 1 710, 1 650, 1 600, 1 520, 1 470,
1 270, 1 175 and 980;
1
HNMR ( CDCl3 ): 0. 88 ( 3
H, t , J= 6. 6 Hz, terminal methyl ) , 1. 25 ( 44H,
br. s, -( CH2 ) 22-) , 1. 64 ( 2H, m , 3’ -H) , 1. 69 ( 2
H, m, 2’ -H) , 3. 93 ( 3H, s, 3-OM e) , 4. 19 ( 2H,
t , J= 6. 7 Hz, 6. 7 Hz, 1’ -H) , 5. 87 ( 1H, br. s,
disappeared when D2O was added, 4-OH) , 6. 30
( 1H, d, J= 16. 0 Hz, 8-H) , 6. 92 ( 1H, d, J= 8. 0
Hz, 5-H) , 7. 04 ( 1H, d, J= 1. 5 Hz, 2-H) , 7. 07
( 1H, dd, J= 1. 5 Hz, 8. 0 Hz, 6-H) , 7. 61 ( 1H,
d, J= 16. 0 Hz, 7-H) ;
13
CNMR ( CDCl3 ): 14. 1
( terminal methy l ) , 22. 7 ( C-n-1) , 26. 0 ( C-3’ ) ,
28. 8～ 29. 7 ( C-4’ -n-3) , 31. 9 ( C-n-2) , 31. 9 ( C-
2’ ) , 55. 9 ( a romatic-OMe ) , 64. 6 ( C-1’ ) , 109. 2
( C-2) , 114. 7 ( C-5) , 115. 7 ( C-8) , 123. 0 ( C-6) ,
127. 0 ( C-1) , 144. 6 ( C-7) , 146. 7 ( C-4) , 147. 9
( C-3) , 167. 4 ( C-9) .
CompoundesⅡ ～ Ⅴ　 The mix t w as obtained
as w hi te pow der; posi tive resul ts wi th FeCl3
reagents, negativ e results wi th Emerson reag-
ents; IR spectrum simila r to tha t of
hexaco sylferula te; the mix t w as dissolv ed in
isopropyl alcoho l and further analy zed by HPLC to
confi rm the existence o f compoundsⅡ～ Ⅴ , whose
retention time w as 8 minutes 12 seconds, 8
minutes 48 seconds, 9 minutes 18 seconds and 10
minutes 36 seconds, respectiv ely. Thei r 1H and 13
CNMR, FAB-M S and HRFAB-M S were show n in
Tables 1, 2.
Table 2.　 FAB-MS and HRFAB-MS data of
compoundsⅡ ～ Ⅴ
compou nd
　
[ M- 1 ]
-
m /z
　
Elemental
composition
　
M easu red
mass
　
Calculated
mass
　
Major
fragments
ions m /z
Ⅰ
　
557
　
C36H61O4
　
557. 459 0
　
557. 457 0
　
193; 175; 161;
148; 133
Ⅱ 529 C34H57O4 529. 427 8 557. 425 7
Ⅲ 543 C35H59O4 543. 443 5 543. 441 3
Ⅳ 571 C37H63O4 571. 474 6 571. 472 6
Ⅴ 585 C38H65O4 585. 490 3 585. 488 3
　 　 Acknow ledgements 　 This w o rk w as
suppo rted by g rants to Dr. J. Z. Deng from the
Natural Science Foundation of China and the
Natural Science Foundation of Jiang su Prov ince.
References
1　 Jiangsu New M edical College. Chinese Medicine Dictionary.
Shanghai: Sh anghai Scien tifi c Technological Publi sher, 1979: 1
298
2　 Tak eya K, et al . Phy toch emis t ry, 1996, 42: 709
3　 Balde A, et al . Phytoch emis t ry, 1991, 30: 102
4　 Chat terjee A, et al . Phy toch emis t ry, 1977, 16: 397
5　 Tezuka Y, et al . Chem Ph arm Bul l, 1989, 37: 3195
6　 Joshi K C, et al . Plan ta M ed, 1986, 25: 71
·88· 中草药　 Ch inese Tradi tional and Herbal Drugs　 2000年第 31卷第 2期
7　 Govindach ari T R, et al . Indian J Ch em, 1971, 9: 1027
8　 Brekhman I I, et al . Ger offen DE3, 641, 495 ( Cl. A61K31 /
70) , 09 Jun 1988, Appl. 04 Dec 1986; 21 pp
9　 M udzhi ri L A, et al . Bri t UK Pat. Appl. GB2, 198, 041
( Cl. A61K31 /195 ) , 08 Jun 1988, GB Appl. 86 /28, 228, 26
Nov 1986; 77 pp
10　 Nair M G, et al . J Ch em Ecol , 1988, 14: 589
11　 Laver M L, et al . J Agric Food Ch em , 1989, 37: 114
( Reciev ed in M ay 15th, 1999)
国产沉香中的三萜成分△
中国科学院华南植物研究所 (广州 510650)　　林立东 　戚树源
摘　要　从国产沉香 Aquilaria sinensis中分得 14个化合物 ,其中羟基何帕酮为首次从该属植物中分到的三
萜化合物 ,在沉香的化学成分研究中 ,尚未见该类化合物的报道。
关键词　国产沉香　化学成分　羟基何帕酮
Triterpenoid from Chinese Eaglewood (Aquilaria sinensis )
South China Institute o f Bo tany , Chinese Academy o f Sciences ( Guang zhou 510650)　 Lin Lidong and Qi Shuyuan
Abstract　　 From Aquilaria sinensis ( Lour. ) Gi lg 14 compounds w ere isolated and identified. Among
them, a triterpenoid 3-oxo-22-hydroxyhopane, w as obtained from this plant fo r the fi rst time. The
presence of t ri terpenoids has no t been repo rted previously a s a chemical constituent of this genus.
Key words　　 Aquilaria sinensis ( Lour. ) Gilg　 chemical consti tuent　 3-oxo-22-hydroxyhopane
　　国产沉香 (又称土沉香 )为瑞香料植物白木香
Aquilaria sinensis ( Lour. ) Gilg含有黑色树脂的木
质部 ,是由于树干损后被真菌侵入后产生。白木香是
我国珍贵的药用植物 ,近年来由于采集沉香供药用 ,
损伤木材极为严重 ,分布较为集中的林木已被破坏
殆尽 ,现仅有零星散生残存植株。主要分布在广东的
高要、陆河、清远等地及海南文昌、琼海等地区 [1 ]。在
对沉香的形成及代谢的研究过程中 ,我们对沉香的
化学成分进行了研究。从国产沉香中分离得到 14个
化合物。分别为:苄基丙酮 ( benzyl acetone) ,对甲氧
基苄基丙酮 ( p -methoxybenzyl acetone) ,沉香螺旋
醇 ( ag arospi rol ) , β -沉香呋喃 (β-aga rofuran) ,二氢
卡拉酮 ( dihydrokarnone) ,白木香醇 ( baimuxin-ol ) ,
去氢白木香醇 ( dehydrobaimuxinol ) ,白木香醛
( baimuxinal ) , kusunol ,羟基 何帕酮 ( 3-oxo-22-
hydroxyhopane) , 6-甲氧基 -2-( 2苯乙基 )色酮 , 6, 7-
二甲氧基-2-( 2苯乙基 )色酮 , 6-甲氧基 -2-[2-( 4’ -甲
氧基苯 )乙基 ]色酮 , 6, 7-二甲氧基 -2-[ 2-( 4’ -甲氧基
苯 )乙基 ]色酮。其中羟基何帕酮为首次从该属植物
中分到的三萜化合物 ,在以前的化学成分报道
中 [2～ 4 ] ,尚未见该类型化合物的报道。羟基何帕醇的
化学结构式见图 1。
1　材料和仪器
图 1　羟基何帕酮的化学结构式
国产沉香购自广东省药材公司。熔点用 MP-S2
显微熔点仪。温度未经校正。 红外光谱用 FTS-185
型仪。核磁共振谱用 DRX-400型核磁共振谱仪。
TM S内标。 EI-M S用 QP-5000型质谱仪。层析用硅
胶为青岛海洋化工厂生产。
2　提取与分离
国产沉香 5 kg打粉 ,用 95%乙醇提取 ,提取液
浓缩后 ,用 5% Na2 CO3溶液皂化 ,再用乙醚提取 ,乙
醚提取液浓缩后得中性部分浸膏。 经反复硅胶层析
分离 ,以石油醚 -乙酸乙酯梯度洗脱和制备 TLC分
离得 14个化合物。
3　结构鉴定
羟基何帕酮的结构: C30 H50O2 ,无色针状晶体 ,
mp 253℃～ 255℃ , M S m /z: 442 ( M+ ) , 424,
409, 384, 381, 369, 313, 245, 207, 205, 189,
149。 IR( KBr ) cm-1: 3 520, 2 920, 1 700, 1 440,
1 375。 1 HNMR( CDCl3 )δ: 0. 77 ( s, 3H) , 0. 96 ( s,
·89·中草药　 Ch inese Tradi tional and Herbal Drugs　 2000年第 31卷第 2期
Address: Lin Lidong, South China Ins ti tute of Botany, Chinese Academy of Sciences , Guangzhou△广东省自然科学基金资助项目 ( 960747)