全 文 ：表 2　化合物Ⅵ的 NMR 数据(CD3OD)
H D JHZ C D
2 6. 26( d) 　 16. 6 1 　 168. 87
3 7. 55( d) 16. 6 2 114. 74
5 7. 05( d) 1. 1 3 146. 45
8 6. 77( d) 8. 1 4 127. 67
9 6. 99( d) 8. 1 5 115. 22
3′ 8. 22( s ) 6 146. 89
4′ 8. 02( d) 6. 5 7 149. 66
5′ 6. 47( d) 6. 5 8 116. 53
1″ 4. 76( d) 2. 8 9 123. 07
1′ 173. 97
2′ 146. 30
3′ 145. 79
4′ 157. 92
5′ 117. 04
1″ 99. 06
2″ 74. 65
3″ 77. 09
4″ 71. 50
5″ 75. 84
6″ 66. 41
h,可明显减少 TN F-A诱导的 CMSMC 对 MNC 的
粘附作用( P< 0. 01)。提示它可能为灯盏花治疗脑
血管疾病的作用机制之一, 这为进一步的药物开发
提供了理论依据。
致谢:质谱由上海医药工业研究院王慧敏高级
工程师测定,核磁共振和红外光谱由第二军医大学
药学院测试中心杨根金老师测定。部分核磁共振工
作由法国图卢兹大学化学系 Merck先生完成。
参考文献:
[ 1]　江苏新医学院 . 中药大辞典[ M ] . 上海: 上海人民出版社,
1997, 948.
[2]　云南第一人民医院 . 治疗瘫痪的中草药——灯盏花[ J ] . 中草
药通讯, 1972, 3( 2) : 47-48.
[ 3]　张卫东,陈万生,王永红, 等 . 灯盏花黄酮苷化学成分的研究
[ J ] . 中草药, 2000, 31( 8) : 565-566.
[ 4] 　施耀曾, 孙祥祯,燕燕灏 . 有机化合物光谱和化学鉴定[ M ] .
南京:江苏科学技术出版社, 1988.
[5]　Yue J M , Lin Z W , Sun H D. A new caf feoly conju gate f rom
E rig eron brev iscapus [ J] . Ch in Ch em Let t , 1997, 8 ( 3) : 225-
227.
[6]　胡昌奇,张德成,李　程 . 灯盏花中一种新的吡喃酮苷 [ J] . 上
海医科大学学报, 1987, 14( 3) : 132.
[7]　徐任生 . 天然产物化学[ M ] . 北京:科学出版社, 1993.
New alkaloid isolated from Fritil laria pallidif lora
ZENG Ling-jie, LI P ing
X
　　( Depar tment o f Pharmacogno sy , China Pharmaceutical Univ ersit y, Nanjing Jiang su 210038, China)
Abstract: Obj ect　To elucidate the structure of a new alkaloid isolated f rom Fr itil laria pallid if lor a
Schrenk. Methods　By means of IR, M S and NMR. Results　T he new alkaloid was ascertained as N -( 1′,
4′-dihydroxy-1′, 2′, 3′, 4′-tet rahydronaphthyl ) -propyl-N -diphenylmethyl-N -3, 3-dimethylbuty lam-
ine. Conclusion　This alkaloid was found for the f irst time fr om the natural plant . It s skeleton and st ruc-
ture is very dif ferent f rom all know n Frit illaria alkaloids.
Key words: Fritil lar ia p all idif lora Schrenk; st ructure elucidat ion; N -( 1′, 4′-dihydroxy-1′, 2′, 3′,
4′-tet rahydronaphthyl ) -propyl-N -dipheny lmethy l-N -3, 3-dimethylbutylam ine
摘　要: 目的　确证从伊贝母中分离得到一种新的生物碱的结构。方法　IR, MS 及 NMR。结果　其结构被鉴定为
N -( 1′, 4′-二羟基-1′, 2′, 3′, 4′-四氢化萘基) -丙基-N -二苯基甲基-N -3, 3-二甲基丁胺。结论　这种生物碱为首次
从植物中分离得到, 它在骨架结构上与已知的贝母生物碱截然不同。
关键词: 伊贝母;结构解析; N -( 1′, 4′-二羟基-1′, 2′, 3′, 4′-四氢化萘基) -丙基-N -二苯基甲基-N -3, 3-二甲基丁胺
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2001) 07 0579 03
1　Introduction
The bulb of Frit illaria plants ( Chinese name
Beimu) is a t radit ional Chinese medicine commonly
used as ant itussive and expecto rant . T he act ive
const ituents o f this medicine ar e the alkaloids con-
f irmed by chem ical and pharmacolo gical studies
[ 1] .
·579·中草药　Chinese T radit ion al and Herbal Dr ugs　2001年第 32卷第 7期
X 收稿日期: 2000-10-12基金项目:国家自然科学基金资助项目( 30070886)作者简介:曾令杰( 1970-) ,男,湖南邵阳人,理学博士。研究方向:中药质量标准及活性成分研究。　Em ail : ljzeng@ soon, com联系作者:李　萍,女,中国药科大学博士生导师、教授,从事中药的活性成分及质量评价研究。
Up to the present , more than a hundred and thirty
alkaloids w ere isolated f rom different Frit illaria
species, and eight of the alkaloids w ere iso lated
fr om Fri tillaria p all idif lora Schrenk
[ 2～5]
. T hough
most of them were iso ster oidal alkaloids, there are
also a few other types of alkaloids such as steroidal
alkaloids et al . T he present paper r eports the
st ructural elucidat ion of a new alkalo id w hich is
very dif ferent f rom the known Friti llar ia alkaloids
either in str ucture o r in alkaloid skeleton.
2　Experiment
2. 1　General pro cedures: M ps: 148. 5℃ unco rr. ,
as determined by a ⅩⅡ-5 apparatus: 1H and 13CN-
MR ( 300 and 75 MHz respect ively ) and 1H-13 C
shift corr elated spect rum wer e reco rded at a Bruker
Am-300 inst rument and T MS in CDCl3 was used as
internal standard. M S spectra w er e measured w ith
ZAB-HS spect rophotometer . IR spectr al data w ere
obtained from a Bio-Rad FT S-135 spectr ometer
w ith KBr pellets. CC w as carried out on Qingdao
silica gel, T LC w as perfo rmed on self prepar ed and
pr ecoated sil ica g el plates.
2. 2　Plant material: T he bulbs of F. p all idif loria
wer e collected in Xinjiang autonomous distr ict of
China, and ident ified by Prof . LI P ing , the vouch-
er specimen is deposited in the Herbarium of China
Pharmaceut ical Univ ersity, Nanjing , China.
2. 3　Ex tr act ion and isolat ion: Ground F . p all idi-
f lora bulbs ( 10 kg ) w ere ex t racted w ith 70% alco-
ho l ( 20 L×3) , and the combined ex t ract w ere con-
centrated to 1 L , af ter adjust ing it s pH to 11. The
so lut ion w as ext racted with chloro form ( 0. 5 L×3)
and the chlor ofo rm layer w as combined and dr ied
under reduced pressure. For ty tw o grams of crude
alkaloid w as obtained. The crude alkaloid w as
chromato graphed on silica g el ( 800 g ) and eluted
w ith cyclohexane-EtOAc-diethylam ine ( 6∶3∶1) .
Three f ract ions w ere obtained and the last f ract ion
w as subjected to silica g el column using chloro-
fo rm-methanol-diethy lamine ( 9 ∶ 1 ∶ 1, low er
phase ) for elut ion. Thus compound Ⅰ ( 100 mg )
w as obtained.
2. 4　CompoundⅠ, C32H 41NO 2, colo rless filamen-
tar y needlem , exhibits po sit iv e reaction to
Dragendorf f s reagent , mp: 148. 5 ℃; IR ( cm- 1 ) ,
3 400 ( br. ) , 2 960, 1 890, 740, 690. EIM S ( m /
z) , ( rel. int ) , 471 ( 23) , 435 ( 5) , 280 ( 100) , 262
( 11) , 183 ( 15) , 105 ( 19) , 96 ( 11) , 85 ( 20) , 77
( 8) , 57 ( 20) , 44 ( 11) . 1HNMR ( T M S in CDCl3 ,
75 Hz) , D 7. 46～7. 51 ( 4H, m , H-6～H-9) , 7. 24
～7. 33 ( 8H, m , H-22, 23, 25, 26, H-28, 29, 31,
32 ) , 7. 16～7. 19 ( 2H, m , H-24, H-30) , 4. 59
( 1H , dd, J= 7. 5 Hz, 2. 5 Hz, H-1) , 3. 14 ( 1H,
d, J= 11 Hz, H-2a) , 2. 97 ( 1H, d, J= 11 Hz, H-
3a) , 3. 06 ( 1H , m , H-20) , 2. 39 ( 2H , m , H-13) ,
1. 29 ( 9H , s, 3CH3 ) . Chemical shift of o ther H
w ere over lapped at D 1. 48～2. 07. 13CNMR, M S in
CDCl 3, D 149. 4 ( C-9) , 146. 1 ( C-21) , 146. 0 ( C-
27) , 142. 7 ( C-10) , 128. 2 ( C-23, C-25, C-29, C-
31) , 126. 4 ( C-5, C-8 ) , 125. 7 ( C-26, C-32 ) ,
125. 4 ( C-6, C-7) , 125. 0 ( C-24, C-30) , 79. 2 ( C-
1) , 73. 4 ( C-4) , 58. 8 ( C-13) , 54. 6 ( C-2) , 53. 3
( C-3) , 41. 2 ( C-20) , 39. 6 ( C-14) , 34. 4 ( C-16) ,
31. 4 ( C-17, C-18, C-19) , 25. 9 ( C-11) , 25. 8 ( C-
12) , 24. 1 ( C-15) .
3　Structure elucidation
Compound Ⅰ, w as obtained as a colorless fil-
ament-like needle, had a formula of C32H41O2 as de-
termined fr om EIMS molecular ion peak at m / z 471
and DEPT data. It show ed a U V maximum at 254
nm indicat ing the presence of phenyl group, w hich
w as conf irmed by IR absorption at 1 800～1 900,
690 and 740 cm
- 1 .
In the EIMS spect rum, M
+
( 471) show ed that
compound Ⅰ was an alkaloid w ith one or odd ni-
trog en, w hich ( M
+ + 1) / M
+ ×100%= 36. 5% and
( M
+
+ 2) / M
+ ×100%= 0. 063% suggests 32 car-
bons and no S, P , X existed in the molecule; the
f ragments of ion peak at m / z 77 and 105 were the
further ev idences fo r the presence o f phenyl groups
in the molecule. T he base peak at m/ z 280 arising
f rom a cleavage indicated that compound Ⅰ was
very different f rom the known Fr itillaria alkaloids
in it s skeletal structure; and the f ragments of m / z
435 ( M
+
- 2H2O) suggested that there w ere tw o
hydroxy g roups in its st ructure as supported by the
signals of methine and methylene linked w ith hy-
droxy at D 79. 2 and 73. 4 in 13 CNMR spect rum .
·580· 中草药　Chinese T radit ion al and Herbal Dr ugs　2001年第 32卷第 7期
The main M S cleavage of compound Ⅰ was shown in Figure 1.
　　DEPT spectr um of compound Ⅰ suggested
thr ee methyls, seven methylenes, 16 methines, six
quaternary carbons in the mo lecule. The assign-
ment of
1
H and
13
CNMR signals o f compound Ⅰ
wer e achiev ed on the basis of 1D and 2D tech-
niques. In the low er field of
13
CNMR, the spectr al
region betw een D 124. 9 and 149. 4 cor relatd w ith D
7. 1 and 7. 5 in the
1
HNMR, w ere the carbon reso-
nances of a tw o-subst ituted and tw o single subst i-
tuted phenyls. The cross peak at D 1. 29/ D 31. 38
w as the signal of three chemically equivalent
methy ls.
The formula C32 H41 NO 2 revealed that com-
pound Ⅰ had 13 ring s and double bonds all togeth-
er ( degree of unsaturation ) , besides the three
pheny l r ings, there remained one ring other than
double bonds evidenced from
1
HNMR.
From the facts above, compoundⅠ can be as-
cer tained as N -( 1′, 4′-dihydroxy-1′, 2′, 3′, 4′-te-
trahydronaphthy l) -propyl-N -diphenylmethyl-N -3,
3-dimethy lbutylam ine. Its st ructure is show n in
Figure 2.
References:
[1]　LI P, XU G J and XU L S. Act ive const ituents of the bulbs of
F rit il laria ebeinsis and their ant itumor activity in mice [ J ] .
Phytotherapy Research, 1995, 9: 560-562.
[ 2]　XU D M, Arih ara S , ZHU ANG Zi-sheng, et al . Isolat ion and
ident if icat ion of yibeinoside A [ J] . Acta Phar maceut ica S ini-
ca, 1990, 25( 10) : 795-797.
[ 3]　XU Y J, XU D M, CU I D B, et al . Is olation and ident if icat ion
of yibeinos ide B [ J ] . Acta Pharmaceu tica S inica, 1993, 28
(3) : 192-196.
[4] 　XU D M , HU ANG E X, WNAG S Q, et al . Stu-dies on the
chemical con st ituents of Fr iti llaria p al lid if l ora [ J] . Acta
Bontanica Sinica 1990, 32( 10) : 789-793.
[ 5]　XU Y J, XU D M, CU I D B, et al . Is olation and ident if icat ion
of yibein os ide C f rom Fri til lar ia p all idif l or a [ J ] . Acta Phar-
maceut ica Sinica 1994, 29( 3) : 200-203.
超临界CO2萃取法与水蒸气蒸馏法提取当归挥发油的比较
李桂生, 马成俊,刘志峰,刘　珂X
(山东省天然药物工程技术研究中心 山东绿叶制药股份有限公司,山东 烟台　264003)
摘　要:目的　考察当归挥发油的不同提取方法。方法　超临界 CO2 流体萃取法及水蒸气蒸馏法。结果　两者的成
分及(Z) -藁本内酯的含量基本一致 ,而超临界 CO 2萃取所得当归油的收率约为水蒸气蒸馏收率的 2 倍。结论　超
临界 CO 2流体萃取法是当归挥发油较好的提取方法。
关键词: 超临界 CO2 流体;水蒸气蒸馏; 当归挥发油
中图分类号: R284. 1　　　文献标识码: A　　　文章编号: 0253 2670( 2001) 07 0581 03
Extraction of essential oil from Angelica sinensis by supercritical-CO2 fluid in
comparison with that by steam distillation
L I Gui-sheng , M A Cheng-jun, L IU Zhi-feng , L IU Ke
　　( Shandong Eng ineering Research Cent er for Nat ur al D rug s, Shandong LUYE Pharm aceutica l CO . , L td. , Yantai Shan-
dong 264003, China)
·581·中草药　Chinese T radit ion al and Herbal Dr ugs　2001年第 32卷第 7期
X 收稿日期: 2001-01-08作者简介:李桂生( 1967-) ,男,河北省衡水市人, 1997年毕业于青岛海洋大学海洋生命学院,获硕士学位。现任职山东省天然药物工程技术研究中心,主要从事于海洋活性物质的研究及中药开发工作。T el : ( 0535 ) 6717618转 8029　　E-m ail : guishen g@ luye-
pharm. com