全 文 ：综合以上数据,确定化合物Ⅰ为 6-甲氧基-7-O-

-D -( 4′-甲氧基)吡喃葡萄糖基香豆素[ 6-methoxy-
7-O-
-D-( 4′-methoxy ) -g lucopyranosy l coumarin] ,
为一新化合物,结构式见图 1。
图 1　化合物Ⅰ的化学结构
Fig. 1　Structure of compound Ⅰ
References:
[ 1]　Xiao P G. N ew ly-comp il ed Rec ord Chinese Materia Med ica
( 新编中药志 ) [ M ] . Vol 4. Bei jing: Ch emical Indus try
Pres s, 2002.
[ 2]　Ch ina Pharmaceut ical University. Col lect ion W ord s of Chi-
nese T radi tional Med icine (中药辞海) [ M ] . Vol 1. Beijing:
Ch ina Medico-Pharmaceut ical Science and T echnology Pub-
lis hing House, 1993.
[ 3]　Li W , Wen H M, Zhan g A H , e t al . Determinat ion of four
nu cleosides an d bases of Bombyx B atryt icarus by HPLC [ J] .
Chin J P harm A nal (药物分析杂志 ) , 1996, 16 ( 6 ) : 406-
407.
[ 4]　Hou Z F, S hi Y P, Li X F, et al . New s teroids f rom
A d enophora st enanthina subsp. xif e ngensis [ J] . I ndian J
Chem, 1997, 3613: 293-296.
[ 5]　Charles J P, J acqlym B. T he A ldr ich L ibr ary of 13C -N MR
and 1H -N MR F IN MR Sp ect ra [ M ] . M ilw aukee Wisc:
Alarich Chemical Co. , 1993.
[ 6]　Zhao Y Q, Yuan C L , Li X, et al . Studies on ch emical con s-
t ituents of A canthop anax gi rald ii [ J] . C hina J Chin Mate r
Med (中国中药杂志) , 1991, 16( 7) : 421-423.
[ 7]　Goodw in H R, Pol lock M B. Ul t raviolet ab sorpt ion spect ra
of coumarin derivat ives [ J] . A rch B iochem Biophy, 1954,
49: 1-6.
Insecticidal active constituents from twig of Aglaia odorata
YANG Si-hai, ZENG Shui-yun
*
, ZHENG Lie-sheng


( Colleg e of Science and T echno lo gy of P lant, Huazhong Ag r icultur al U niver sity , Wuhan 430070, China)
Abstract: Object　T o study the insect icidal activity const ituents f rom the tw ig s of tr aditional Chinese
fo lk medicine “Mizilan”or “Shu-Lan”( A glaia odor ata Lour. ) . Methods　Seperat ion and purif icat ion un-
der bio assay-directed w er e per formed on silica g el CC, Sephadex LH-20 CC and preparat ive TLC. T heir
st ructures w ere established on the basis of phy sico chem ical and spect ral analysis. Results　Seven com-
pounds w ere isolated and ident if ied as rocaglamide (Ⅰ ) , desmethy l rocaglamide (Ⅱ ) , 8-methoxy-
marikar in (Ⅲ ) , 7-hydro xy-6-methoxy-coumarin (Ⅳ ) , 3′-hydroxy-methy lrocaglate (Ⅴ ) , 3′-hydroxy-
rocag lamide (Ⅵ) , marikar in (Ⅶ) , respect ively. Conclusion　Compound Ⅳ is isolated fr om the plant of
A glaia Lour. fo r the f ir st t ime and compounds Ⅲ and Ⅶ ar e isolated from A . od orata fo r the first t ime.
Key words : A glaia odor ata Lour. ; insect icide; chemical const ituent
米仔兰枝条中杀虫活性成分研究
杨四海,曾水云,郑烈生
(华中农业大学植物科技学院,湖北 武汉　430070)
摘　要: 目的　研究中国传统民族植物药米仔兰(又称树兰) A glaia odorata Lour . 枝条中杀虫活性成分。方法　以
生物测定为指导, 采用硅胶柱、Sephadex LH-20柱以及制备薄层分离板对其成分进行分离和纯化,并通过物化性质
和光谱分析对其结构鉴定。结果　从中分离得到 7 个化合物, 分别鉴定为 r ocag lamide (Ⅰ)、desmethy l ro caglamide
(Ⅱ)、8-methoxymarikarin (Ⅲ)、7-羟基-6-甲氧基-香豆素 (Ⅳ )、3′-hydroxy-methy lr ocag la te (Ⅴ )、3′-hydroxy-
rocaglamide (Ⅵ)、mar ikar in (Ⅶ)。结论　化合物Ⅳ为首次从 A glaia Lour . 属植物中分离得到,化合物Ⅲ和Ⅶ为首
次从米仔兰植物中分离得到。
关键词: 树兰;杀虫; 化学成分
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2004) 11 01207 05
·1207·中草药　Chinese T radit ional and Herbal Drugs　第 35 卷第 11 期 2004年 11 月
收稿日期: 2004-03-15作者简介:杨四海( 1973- ) ,男,湖北汉川人,助理研究员,理学硕士, 1999 年毕业于南开大学化学系有机化学专业,主要从事药物合成和天然产物化学研究。　E-mail: yangs ihai@yahoo. com
* 通讯作者　E-mail: zengsy @m ail . hzau. edu . cn
　　A glaia od orata Lour. , a slow-g row ing mem-
ber of M eliaceae, nat ive to China but w idely cult i-
vated thr oughout M alaysia and Thailand, is a
fav our ite o f the Chinese on account of it s f ra-
grance. T he flow ers are used to perfume clothes
and for scent ing tea. It also f igures prom inent ly in
t radit ional folk pharmacopeias throughout South-
east Asia . Known as Mizilan o r Shu-Lan in Fujian
and Taiw an Provinces o f China, it has been used as
a herbal r emedy for t reatment of human cough, in-
flammat ion and traumat ic injury in Chinese Folk-
lore. In T hailand the same plant is traditionally
pr escribed as a heart st imulant and febrifug e, and
as an expecto rant .
Fo r the past two decades, in Thailand and
Vietnam, a series of rocaglamide derivatives w hich
featur ed the cyclopentatet rahydrobenzofuran skele-
ton had been isolated from several species of the
A glaia Lour. , and w ere show n to exhibit the in-
sect icidal act ivity
[ 1-7] . T his act iv ity reported for the
rocaglamide congener s is comparable to that of
azadiracht in, a pow erful natural insect icide that is
of considerable commercial interest and has
pr ompted us to screen for further act ive deriv a-
tiv es. In order to search for new potent ial insectici-
dal compounds of plant orig in and compar e the
chemical const ituents of A . odor ata. cult ivated in
China w ith w hich cult ivated at abro ad, the insect i-
cidal const ituents o f the tw ig s of t radit ional Chi-
nese fo lk medicine “Shu-Lan”( A . od orata) had
been studied. Seven compounds f rom the crude
methanolic ex t racts o f sw igs of A . odorata were
isolated by bioassay-guided fractionat ion and iden-
tical as rocaglamide (Ⅰ) , desmethyl ro caglam ide
( Ⅱ ) , 8-methoxymarikarin ( Ⅲ ) , 7-hydroxy-6-
methoxy-coumarin (Ⅳ) , 3′-hydr oxy-methy lroca-
glate ( Ⅴ ) , 3′-hydroxyro caglam ide ( Ⅵ ) ,
marikarin (Ⅶ) , respectiv ely . Among them, com-
pound Ⅳ was isolated f rom the plants of Aglaia
Lour. fo r the first t ime and compounds Ⅲ and Ⅶ
wer e isolated from A . od orata fo r the first t ime.
1　Instruments and materials
NMR spectra w ere recorded on Bruker DRX-
400 MHz spect rometers. EI-M S spect ra ( 70 eV)
w ere obtained by direct inlet on a HP 5970 mass
spectrometer . Optical r otat ion w as WXG - 4 po-
larimeter. M ps w ere carried out using a B - 545
mel ting point appar atus. CC: silica gel ( 200- 300
mesh, from Qingdao M ar ine Chemical Factory ) .
Sephadex LH-20 ( Pharmacopia 17-0090-01) .
T he stw ig s o f A . odorata was collected in
Wuyishan, Fujian Prov ince, China and ident if ied
by Dr . WANG Wei-feng in M ay of 2001.
2　Extraction and isolation
Air -dried and powder ed tw ig s of A . odorata
( 2. 5 kg ) w ere ground and ext racted w ith M eOH
( 12 L×2) at room temper ature for two day s. T he
methano lic ex t ract was concentrated to 1 L in vac-
uo, diluted w ith an equal volumn of H2O, and ex-
tracted successiv ely w ith hexane ( 500 mL×3) , E-
tOAc ( 500 mL×3) and water saturated n-butano l,
r espect ively. Each obtained fr act ion w as subjected
to a bio assay w ith neonate larvae o f S. littoralis.
F rom this bioassay the insecticidal activity w as
found to reside in the EtOAc fraction. The EtOA c
fract ion w as concentrated to 100 mL in vacuo , di-
luted w ith 100 mL 5% NaOH solution, and ex-
tracted successively w ith Et 2O ( 200 mL×3) . T he
Et 2O solut ion w ashed with H2O ( 200 mL ) , and
dried w ith anhydrous. Na2SO 4 , and evapor ated in
vacuo to g iv e a pale brow nish gum ( 17. 3 g) . Isola-
t ion of the compounds from the pale br ow nish gum
was accomplished by repeated chr omatogr aphic
separat ion emplo ying silica g el ( mobile phase:
CH2Cl 2-iso-PrOH 95∶ 5 and 90/ 10) , Sephadex
LH-20 ( M e2CO ) . Fractions were monitored by
T LC on pr ecoated TLC plates w ith silica gel 60
F 254 ( mobile phase: CH2Cl2-iso-PrOH 95∶5 or hex-
ane-iso-PrOH-EtOAc 9∶1∶1) or after spraying
w ith anisaldehyde reagent . F inal purification w as
obtained using preparat ive T LC [ silica gel 60 F254 ,
CH2Cl 2-EtOAc-MeOH ( 75∶20∶5) , or EtOA c-
M eOH ( 45∶1) ] . Yields of compounds were Ⅰ:
13. 2 mg ; Ⅱ: 6. 3 mg ; Ⅲ: 7. 4 mg .
T he NaOH solution w as acidif ied w ith diluted
HCl and ext racted w ith Et 2O ( 200 mL×3) , the
Et 2O layer w as evapo rated in vacuo. Isolat ion of
the compounds f rom the residue w as accomplished
·1208· 中草药　Chinese T radit ional and Herbal Drugs　第 35 卷第 11 期 2004年 11 月
by repeated chromatographic separat ion employ ing
silica gel ( mobile phase: CH2Cl2-iso-PrOH 90∶
10) , Sephadex LH-20 ( M e2CO) . Fract ions w ere
monitored by T LC on precoated TLC plates w ith
silica gel 60 F254 ( mobile phase: CH2Cl2-iso-PrOH
90∶10 or hexane-iso-PrOH-EtOAc 8∶1∶1) or
after spray ing w ith anisaldehyde reagent . Final pu-
rificat ion w as obtained using pr eparativ e T LC [ sili-
ca gel 60 F254 , CH2Cl2-EtOAc-M eOH ( 70∶25∶
5) , or EtOAc-MeOH ( 40∶1) ] . Yields of com-
pounds w ere Ⅳ: 15. 6 mg ; Ⅴ: 7. 4 mg ; Ⅵ: 10. 5
mg ; and Ⅶ: 5. 3 mg.
3　Experiments with insects
Larvae of S . litoralis were f rom a laboratory
co lony reared on an art ificial diet under controlled
condit ions at 26 ℃. Feeding studies w ere conduct-
ed w ith neonate larvae ( n= 20 fo r each treatment ) .
Neonate lar vae w ere kept on diets containing ex-
tr acts under study . Af ter six days, survival and
w eight o f sur vived larv ae w ere recor ded and com-
pared w ith the contro ls.
4　Structure elucidation
Compound Ⅰ: Pale y ellow powder, mp 115-
117 ℃ ( CHCl 3 ) . [
] 20D - 89. 0°( CHCl3 ) . EI-M S
m/ z ( % ) : 505 [ M ]
+
( 5) , 478 ( 12) , 390 ( 51) ,
313 ( 55) , 300 ( 69) , 285 ( 24) , 205 ( 17) , 181
( 22) , 176 ( 100) , 135 ( 11) , 131 ( 14) , 103 ( 61) ,
77 ( 62) , 72 ( 95) , 55 ( 71) , 44 ( 54) . 1H-NMR
( acetone-d6 ) :
2. 71 ( 1H, br, s, OH ) , 2. 76 ( 1H,
br, s, OH ) , 2. 89 ( 3H, s, N -M e) , 3. 41 ( 3H, s,
N-M e) , 3. 82 ( 3H, s, O-M e) , 3. 88 ( 3H, s, O-
M e) , 3. 91 ( 3H, s, O-M e) , 4. 13 ( 1H , dd, J=
6. 6, 13. 2 Hz, H-2) , 4. 51 ( 1H, 13. 6 Hz, H-3) ,
4. 96 ( 1H, 6. 6 Hz, H-1) , 6. 25 ( 1H, 1. 4 Hz, H-
5) , 6. 37 ( 1H, d, 1. 4 Hz, H-7) , 6. 72 ( 2H, d, 8. 9
Hz, H-3′和 H-5′) , 6. 86 - 7. 05 ( 5H, m, H-2′-
6″) , 7. 16 ( 2H, d, 8. 9 Hz, H-2′和 H-6′) .
13
C-NMR ( acetone-d6) :
34. 7, 36. 2 ( 2×N-Me) ,
42. 9 ( C-2) , 55. 4, 55. 7, 56. 3 ( 3×OMe ) , 57. 2
( C-3) , 79. 1 ( C-1) , 89. 7 ( C-5) , 93. 4 ( C-7) ,
94. 9 ( C-8b) , 102. 7 ( C-3a) , 109. 8 ( C-8a) , 114. 7
( C-3′, 5′) , 126. 1 ( C-4″) , 127. 6 ( C-2″, 6″) ,
128. 9 ( C-3″, 5″) , 130. 6 ( C-1′) , 131. 1 ( C-2′,
6′) , 140. 4 ( C-1″) , 158. 1, 158. 9, 159. 2, 162. 4
( C-4′, 4a, 6, 8) , 172. 5 ( C= O) . Compar ing w ith
the reported data, the st ructure of compound Ⅰ
was identif ied as rocaglamide[ 1 , 2] .
Compound Ⅱ: Pale yellow powder; mp 117-
119 ℃( CHCl3 ) . [
] 20D - 54. 7°( CHCl3 ) . EI-M S m/
z ( %) : 491 [ M ]
+ ( 8) , 473 ( 15) , 390 ( 51) , 313
( 59) , 301 ( 84) , 300 ( 100) , 285 ( 41) , 242 ( 56) ,
191 ( 36) , 181 ( 53) , 162 ( 89) , 131 ( 44) , 162
( 96) , 77 ( 45) , 58 ( 74) . 1H-NMR ( CDCl3 ) :

2. 01 ( 1H, br, s, OH) , 2. 69 ( 3H, s, N -M e ) ,
3. 57 ( 1H, br, s, OH ) , 3. 78 ( 3H , s, O-M e ) ,
3. 81 ( 3H , s, O-M e) , 3. 85 ( 3H, s, O-Me) , 3. 92
( 1H, dd, J = 5. 8, 14. 6 Hz, H-2) , 4. 29 ( 1H, 14. 6
Hz, H-3) , 4. 88 ( 1H, 5. 8 Hz, H-1) , 6. 23 ( 1H, d,
2. 1 Hz, H-5) , 6. 34 ( 1H, d, 2. 1 Hz, H-7) , 6. 68
( 2H , d, 9. 5 Hz, H-3′和 H-5′) , 6. 98- 7. 06 ( 5H,
m , H-2′- 6″) , 7. 12 ( 2H, d, 9. 5 Hz, H-2′和 H-
6′) . 13C-NMR ( CDCl3 ) :
26. 9 ( N-M e) , 52. 9 ( C-
2) , 55. 8, 56. 2, 56. 3 ( 3×OMe ) , 56. 8 ( C-3) ,
80. 3 ( C-1) , 89. 3 ( C-5) , 93. 1 ( C-7) , 95. 4 ( C-
8b) , 103. 1 ( C-3a ) , 109. 9 ( C-8a ) , 113. 6 ( C-3′,
5′) , 126. 4 ( C-4″) , 129. 5 ( C-2″, 6″) , 129. 9 ( C-
3″, 5″) , 130. 3 ( C-1′) , 131. 4 ( C-2′, 6′) , 139. 5
( C-1″) , 158. 4, 158. 7, 160. 9, 163. 7 ( C-4′, 4a,
6, 8) , 173. 8 ( C= O ) . All of these data w er e in
good agreement w ith tho se repo rted data of des-
methyl ro caglam ide, so compound Ⅱ was ident i-
f ied as desmethyl rocaglamide
[ 2]
.
Compound Ⅲ: Colourless oil . [
] 20D - 49. 9°
(CHCl3 ) . EI-M S m/ z ( %) : 524 [ M ]
+ ( 47) , 506
( 27) , 389 ( 74) , 370 ( 100) , 343 ( 19) , 313 ( 42) ,
285 ( 41) , 135 ( 46) , 77 ( 41) , 58 ( 63) .
1
H-NMR
( CDCl3) :
2. 37 ( 1H, m , H-3
B) , 2. 41 ( 1H, m ,
H-3
A ) , 2. 72 ( 1H, br , s, OH) , 3. 17 ( 1H, m ,
H-4
B) , 3. 29 ( 1H, m , H-4
A ) , 3. 74 ( 3H, s,
OM e-4′) , 3. 79 ( 3H, s, OM e-8) , 3. 82 ( 3H, s,
OM e-6) , 4. 12 ( 1H, m, H-2
B) , 4. 19 ( 1H, m ,
H-2
A) , 4. 51 ( 1H, s, H3-H) , 6. 19 ( 1H, d, 2. 0
Hz, H-7) , 6. 36 ( 1H, d, 2. 0 Hz, H-5) , 6. 54 ( 2H,
d, 9. 2 Hz, H-3′和H-5′) , 6. 84- 7. 02 ( 5H, m , H-
2′- 6″) , 7. 09 ( 2H , d, 9. 2 Hz, H-2′和 H-6′) .
13C-NMR ( CDCl3 ) :
19. 7 ( C-3
) , 34. 7 ( C-4
) ,
50. 2 ( C-2
) , 55. 1, 55. 9, 56. 1 ( 3×OM e) , 59. 4
( C-3) , 92. 4 ( C-7) , 94. 1 ( C-5) , 96. 6 ( C-8b ) ,
·1209·中草药　Chinese T radit ional and Herbal Drugs　第 35 卷第 11 期 2004年 11 月
105. 4 ( C-3a) , 108. 9 ( C-8a ) , 113. 8 ( C-3′, 5′) ,
120. 4 ( C-2) , 127. 6 ( C-4″) , 128. 3 ( C-3″, 5″) ,
129. 2 ( C-1′) , 130. 4 ( C-2′, 6′) , 131. 5 ( C-2″, 6″) ,
139. 1 ( C-1″) , 159. 4, 159. 7, 162. 3, 164. 8 ( C-4′,
4a, 6, 8) , 161. 8 ( C-1) , 167. 2 ( C-5
) , 171. 5
( C= O ) . Comparing w ith the reported data, the
st ructure o f compound Ⅲ was ident ified as 8-
methoxymarikar in
[ 3]
.
Compound Ⅳ: Colour less needle crystals. mp
204- 206 ℃ ( CHCl3 ) . It show ed blue fluorescence
under UV 254.
1
H-NMR ( CDCl 3) :
3. 91 ( 3H , s,
OCH 3-6) , 6. 29 ( 1H, d, 9. 2 Hz, H-3) , 7. 65 ( 1H,
d, 9. 2 Hz, H-4) , 6. 81 ( 1H , s, H-8) , 6. 97 ( 1H,
s, H-5) , 6. 28 ( 1H , brs, OH) . EI-MS m/ z ( %) :
192 [ M ]
+
( 100) , 177 ( 44) , 164 ( 21) , 149 ( 19) ,
121 ( 39) , 79 ( 62) , 69 ( 51) . By compar ing its mp,
1H-NMR, EI-M S, and Rf values w ith tho se of the
authent ic sample, the compound Ⅳ was ident if ied
as 7-hydr oxy-6-methoxy-coumarin.
Compound Ⅴ: Pale y ellow powder; mp 124-
126 ℃( CHCl3 ) . [
] 20D - 55. 1°( CHCl3 ) . EI-M S
m/ z ( % ) : 508 [ M ]
+ ( 6) , 490 ( 20) , 406 ( 17) ,
329 ( 27) , 316 ( 100) , 301 ( 41) , 283 ( 34) , 218
( 14) , 181 ( 19) , 77 ( 51) , 58 ( 67) .
1
H-NMR ( CD-
Cl3 ) :
2. 45 ( 1H, br , s, OH) , 2. 89 ( 1H, br, s,
OH) , 3. 69 ( 3H, s, CO-OCH3 ) , 3. 74 ( 3H, s,
OCH 3-4′) , 3. 82 ( 3H , s, OCH3-8) , 4. 07 ( 1H, dd,
14. 3, 6. 6 Hz, H-2) , 4. 26 ( 1H, d, 14. 3 Hz, H-3) ,
4. 91 ( 1H, d, 6. 6 Hz, H-1) , 6. 19 ( 1H, d, 1. 9
Hz, H-5) , 6. 32 ( 1H , d, 1. 9 Hz, H-7) , 6. 64 ( 1H,
d, 8. 2 Hz, H-5′) , 6. 71 ( 1H, dd, 2. 1, 8. 2 Hz, H-
6′) , 6. 82 ( 1H, d, 2. 1 Hz, H-2′) , 6. 94 - 7. 04
( 5H, m, H-2″- 6″) , 12. 69 ( 1H, br , s, Ar-OH) .
13
C-NMR ( CDCl3 ) :
52. 4 ( C-2) , 53. 6 ( CO-
CH3 ) , 55. 9, 56. 1, 56. 4 ( 3×OMe) , 57. 2 ( C-3) ,
81. 4 ( C-1) , 90. 7 ( C-5) , 93. 6 ( C-7) , 95. 2 ( C-
8b ) , 102. 5 ( C-3a ) , 109. 4 ( C-8a) , 112. 2 ( C-5′) ,
116. 3 ( C-2′) , 121. 7 ( C-5′) , 127. 9( C-4″) , 129. 1
( C-3″, 5″) , 130. 3 ( C-2″, 6″) , 130. 9 ( C-1′) ,
139. 3 ( C-1″) , 145. 3 ( C-3′) , 148. 4, 158. 9,
161. 3, 164. 7 ( C-4′, 4a, 6, 8) , 172. 1 ( C= O) .
Comparing w ith the r eported data, the st ructure of
compound Ⅴ was ident if ied as 3′-hydroxy-methyl-
rocag late
[ 6]
.
Compound Ⅵ: Pale yellow powder; mp 126-
129 ℃( CHCl 3 ) . [
] 2 0D - 89. 8°( CHCl 3 ) . EI-M S
m / z ( %) : 521 [ M ] + ( 11) , 503 ( 31) , 406 ( 62) ,
329 ( 59) , 316 ( 78) , 301 ( 21) , 283 ( 13) , 181
( 57) , 176 ( 100) , 131 ( 23) , 77 ( 44) , 58 ( 61) .
1
H-NMR ( CDCl3 ) :
2. 37 ( 1H , br , s, OH ) , 2. 74
( 1H, br, s, OH) , 2. 96 ( 3H, s, N-M e ) , 3. 44
( 3H, s, N-M e) , 3. 81 ( 3H , s, OCH3-4′) , 3. 84
( 3H , s, OCH3-6) , 3. 93 ( 3H , s, OCH3-8) , 4. 13
( 1H, dd, 13. 9, 7. 2 Hz, H-2) , 4. 37 ( 1H , d, 13. 9
Hz, H-3) , 4. 92 ( 1H, d, 7. 2 Hz, H-1) , 6. 24 ( 1H,
d, 1. 9 Hz, H-5) , 6. 36 ( 1H, d, 1. 9 Hz, H-7) ,
6. 66 ( 1H , d, 8. 6 Hz, H-5′) , 6. 77 ( 1H, dd, 2. 3,
8. 6 Hz, H-6′) , 6. 84 ( 1H, 2. 3 Hz, H-2′) , 6. 90-
7. 06 ( 5H, m , H-2″- 6″) , 12. 49 ( 1H, br, s, Ar-
OH) .
13
C-NMR ( CDCl 3 ) :
28. 2 ( N -M e) , 34. 8
( N -Me ) , 39. 5 ( C-2) , 55. 4, 55. 7, 56. 2 ( 3×
OM e ) , 57. 4 ( C-3) , 80. 7 ( C-1) , 89. 6 ( C-5) ,
92. 9 ( C-7) , 96. 1 ( C-8b ) , 102. 7 ( C-3a ) , 110. 3
( C-8a) , 113. 4 ( C-5′) , 116. 9 ( C-2′) , 120. 7 ( C-
6′) , 127. 3 ( C-4″) , 128. 9 ( C-3″, 5″) , 129. 6 ( C-
2″, 6″) , 130. 4 ( C-1′) , 140. 1 ( C-1″) , 146. 4 ( C-
3′) , 147. 4, 159. 9, 163. 3, 165. 2 ( C-4′, 4a , 6,
8) , 172. 1 ( C= O) . All o f these data w er e in good
ag reement w ith tho se r eported data of 3′-hydroxy-
rocaglam ide, so compound Ⅵ was identif ied as 3′-
hydroxyro caglam ide
[ 3] .
Compound Ⅶ: Colourless oil . [
] 20D - 44. 9°
(CHCl3 ) . EI-M S m/ z ( %) : 510 [ M ]
+
( 25) , 494
( 23) , 492 ( 67) , 415 ( 82) , 370 ( 100) , 343 ( 11) ,
341 ( 47) , 135 ( 26) , 77 ( 54) , 58 ( 59) . 1H-NMR
( CDCl3) :
2. 31 ( 1H, m , H-3
B) , 2. 37 ( 1H, m ,
H-3
A ) , 2. 92 ( 1H, br , s, OH) , 3. 21 ( 1H, m ,
H-4
B) , 3. 28 ( 1H, m , H-4
A ) , 3. 71 ( 3H, s,
OM e-4′) , 3. 74 ( 3H, s, OM e-6) , 4. 09 ( 1H, m ,
H-2
B) , 4. 14 ( 1H, m , H-2
A) , 4. 62 ( 1H, s, H-
3) , 6. 11 ( 1H, d, 1. 9 Hz, H-7) , 6. 28 ( 1H , d, 2. 0
Hz, H-5) , 6. 59 ( 2H, d, 8. 9 Hz, H-3′和 H-5′) ,
6. 94- 7. 09 ( 5H, m , H-2′- 6″) , 7. 14 ( 2H, d, 8. 9
Hz, H-2′和 H-6′) , 12. 18 ( 1H, br, s, Ar -OH ) .
13
C-NMR ( CDCl3 ) :
18. 4 ( C-3
) , 33. 8 ( C-4
) ,
49. 4 ( C-2
) , 55. 1 ( OM e-4′) , 56. 2 ( OM e-6 ) ,
59. 9 ( C-3) , 91. 3 ( C-7) , 92. 7 ( C-5) , 95. 8 ( C-
8b) , 104. 1 ( C-3a ) , 107. 2 ( C-8a ) , 113. 1 ( C-3′,
·1210· 中草药　Chinese T radit ional and Herbal Drugs　第 35 卷第 11 期 2004年 11 月
5′) , 121. 4 ( C-2′) , 126. 3 ( C-4″) , 127. 0 ( C-3″,
5″) , 128. 8 ( C-1′) , 129. 5 ( C-2′, 6′) , 130. 5 ( C-
2″, 6″) , 137. 4 ( C-1″) , 157. 2, 160. 8, 165. 6 ( C-
4′, 4a, 6, 8) , 162. 4 ( C-1) , 167. 7 ( C-5
) , 170. 1
( C= O) . Comparing w ith the r eported data, the
st ructure of compound Ⅶ was identif ied as
marikarin[ 7] .
Acknowledgements: We thank Prof. DENG
Guo-cai ( from Department of Chemistry, Nankai
University, China) f or helpful discussions and
some useful advices.
References:
[ 1]　Fiichi F, Masaito O, M ing L K, et al . 1H-Cyclopenta [ b ]
ben zofu ran derivat ive and i ts analog [ P] . US : 4 539 414,
1985-09-03.
[ 2]　Fum ito I, Chutamas S , Murray, et al . Insect icidal 1H-Cy-
clopentatet rahydro [ b ] b enzofurans from Ag laia od or ata
[ J ] . P hy toch emistry, 1993, 32( 2) : 307-310.
[ 3]　Nug roho B W , E drada R A, Gu ssr egen B, e t al . Ins ect icidal
rocaglamide derivat ives f rom A glaia dupp ereana [ J] . Phyto-
chemist ry, 1997, 44( 8) : 1455-1461.
[ 4]　Vin cen t D, Odile T, Olam rew aju R, et al . New nit rogenous
and arom at ic derivat ives f rom A glaia arg entea an d A . f orbe-
sii [ J ] . T etr ahedr on, 1996, 52: 6931-6942.
[ 5]　Baoliang C, Heebyun g C, T hawatch ai S . Novel cytotox ic
1H-cyclopenta [ b] b enzofuran l ignans f rom A glaia el lip t ica
[ J ] . T etr ahedr on, 1997, 53: 17625-17632.
[ 6]　Chaidir H J , N ugroho B W. New in sect icidal rocaglamide
derivat ives fr om f low er s of A glaia dupe rreana [ J] . Phyto-
chemist ry, 1999, 52: 837-842.
[ 7]　Harald G, Thom as P, Brigit t e B. Ins ect icidal f lavagl ines and
other com pounds f rom F ij ian Ag laia species [ J] . Phyto-
chemist ry, 2001, 57: 57-64.
中国南海海绵正丁醇部分中的核苷类成分研究
季宇彬1 ,王　禹1, 2,林文翰2

( 1. 哈尔滨商业大学 博士后工作站, 黑龙江 哈尔滨　150040; 2. 北京大学
医学部天然药物及仿生药物国家重点实验室, 北京　100083)
摘　要: 目的　对中国南海产海绵 Cinachy r ella austr aliensis 的正丁醇部分化学成分进行了系统分离,为合理开发
海洋药物资源, 更好地利用海洋生物体内具有强生理活性的化学成分, 从而开发出适用于人体的安全有效的药物。
方法　采用多种色谱方法进行分离纯化, 应用波谱分析技术,并结合文献对照,对所分离到的化合物进行了结构鉴
定。结果　共分离得到 7 个化合物,其结构分别为: 2-甲基-6-氨基嘌呤脱氧核苷[ 2-met hy l-6-amino-9-( 2-deoxy-
-
D-r ibofur ano syl) -pur ine, Ⅰ]、6-氨基嘌呤脱氧核苷( 2′-deoxyadenosne, Ⅱ)、6-氨基嘌呤核苷( 6-amino-9-
-D-ribo-
fur anosy l-9H-punne, Ⅲ)、尿嘧啶( ur acill, Ⅳ)、胸腺嘧啶( thymine, Ⅴ)、胸腺嘧啶脱氧核苷( t hymidine, Ⅵ)、尿嘧
啶脱氧核苷[ 1-( 2-deoxy-
-D-ribo furanosy l) ur acil, Ⅶ]。结论　对中国南海海绵正丁醇部分的化学成分进行了报
道, 系统地分离出了 2 大类核苷类化合物。
关键词: 海绵;分离提取; 结构鉴定
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2004) 11 01211 03
Study on nucleotidoids from n-butyl alcohol part of sponge Cinachyrella australiensis
JI Yu-bin
1 , WANG Yu
1, 2 , L IN Wen-han
2
( 1. Doctorpo stal Pr og ramm , School o f Pharmaceutical Institut e, Harbin U niver sity of Commerce, Harbin 150040, China;
2. State Key Labor ato ry of Natur al and Biomim etic Drug s, Peking Univ ersity, Beijing 100083, China)
Abstract: Object　To search for bio act ive secondary metabo lites f rom mar ine o rganisms, the marine
sponge Cinachyr ella aust ral iensis was co llected fr om Hainan Island, Souther n China Sea to develop the ef fi-
cient dr ug fo r human beings. Methods　Silic g el flash chromatog raphy in asso ciat ion w ith rev er se phase
semipreparat ive HPLC was per formed for the iso lation and purification o f the ethanol ext racts, and ex ten-
sive spectr oscopy including 2D NMR spect ra as w ell as the comparison of the spect ral data w ith tho se re-
por ted in literatures w as applied for the str ucture elucidation. Results　Seven nucleot idoids w ere isolated
·1211·中草药　Chinese T radit ional and Herbal Drugs　第 35 卷第 11 期 2004年 11 月

收稿日期: 2004-04-20基金项目:国家科技部海洋 863研究课题( 2001AA620403, 2002AA217081)作者简介:季宇彬( 1956- ) ,男,哈尔滨商业大学教授,博士生导师,从事天然产物抗肿瘤方面的研究。　T el : ( 0451) 84866001