全 文 ：Norditerpenoid Alkaloids from Aconitum carmichaeli
var.hwangshanicum
ZHAO An-Xing , PENG Chong-Sheng＊ ,ZHANG Chen-Hong , JIA Wei
School of Pharmacy , Shanghai Jiaotong University , Shanghai 200240 , China
【ABSTRACT】　AIM:To study the diterpenoid alkaloids of the radix of Aconitum carmichaeli var.hwangshanicum.
METHOD:The total alkaloids obtained by ion exchange resin were subjected to chromatography to afford three norditerpenoid
alkaloids.Their structures were elucidated mainly by spectroscopic methods.RESULTS:Three major compounds:hypaconi-
tine(1), mesaconitine(2), neoline (3)have been isolated from Aconitum carmichaeli var.hwangshanicum.CONCLU-
SION:Compounds 1～ 3 have been obtained from Aconitum carmichaeli var.hwangshanicum for the first time.Compounds 1
and 2 containing C(14)-benzoate and C(8)-acetate group were major alkaloids in this plant.
【KEY WORDS】　Aconitum carmichaeli var.hwangshanicum;Norditerpenoid alkaloids
【CLCNumber】　R284.1　　【Document code】　A 　　【Article ID】　1672-3651(2007)05-0355-02
【Received on】　2007-06-12
【Foundation Item】　This project was supported by PRP of Shanghai
Jiaotong University (No.17006).
【＊Corresponding author】　PENG Chong-Sheng:Associate Professor ,
Tel:86-21-34204945 , E-mail:cspeng@sjtu.edu.cn
　　There are 250 species in Aconitum family plants in
our globe , of which 120 are grown in China.Many of
these plants were used as traditional Chinese medicines.
Diterpenoid alkaloids are the pharmacologically active
ingredients in Aconitum sp.plants.A.carmichaeli
var.hwangshanicum is a medicinal plant grown in
Huangshan Mountain area , Anhui , northwest Zhejiang
and northeast Jiangxi province of China
[ 1 , 2] .The radix
of the plant has been used in treating injuries , swelling ,
and pain by local people
[ 2 , 3]
for years , but the chemical
components of this plant have not been reported yet.
During our investigation of chemical constituents of A.
carmichaeli var.hwangshanicum , three norditerpenoid
alkaloids were isolated and elucidated as hypaconitine
(1), mesaconitine(2), neoline (3).Compounds 1 ～
3 are also major active components in Chinese herbs
named “Caowu”[ 4] .
1　Apparatus and Reagents
X-4 micro-melting point apparatus (uncorrected);
WZZ-2B polarimeter;Agilent 1100 series LC MSD Trap
mass spectrometer;Varian NMR spectrometers operating
at 400 MHz for
1
H (125 MHz for 13 C)in CDCl3 with
TMS as the internal standard.Silica gel H and GF254
(Qingdao Marine Chemical Factory);Modified Dragen-
dorff s reagent;Polyvinyl sulfonic ion exchange resin
(H form , cross link 1 × 1 , Huazhen Company ,
Shanghai , China).
2　Plant Material
The radix of A.carmichaeli var.hwangshanicum
was collected in Huangshan , Anhui province , China ,
in September 2004 , and identified by Prof.Wang De-
qun.A voucher specimen has been deposited at the
School of Pharmacy , Shanghai Jiaotong University.
3　Extraction and Isolation
According to the the literature
[ 5]
method , air-dried
and powdered radix of Aconitum carmichaeli var.
hwangshanicum (1.0 kg)was percolated with 0.2%
HCl(12 L).The percolate was added to polyvinyl sul-
fonic ion exchange resin(dry weight 10 kg)to give total
alkaloids(5.1 g)as yellowish powder.The total alka-
loids(4.6 g)were then subjected to repeated silica gel
column chromatography eluted with CHCl3-MeOH to af-
ford compounds 1(400 mg), 2(290 mg)and 3 (70
mg).
　2007年 9月　第 5卷　第 5期 Chin J Nat Med　Sep.2007　Vol.5　No.5　355　
4　Structure elucidation
Compound 1　colorless crystal , mp 196 ～ 198 ℃;[α] D+
32°(c 0.50 , CHCl3);ESI-MS(+)m z 616 [ M + H] +.1H
NMR(400 MHz , CDCl3)δ:1.35 (3H , s , COCH3), 2.32
(3H , s , NCH3), 2.34 , 2.53 (each 1H , ABq , J =10.9 Hz ,
H-19), 3.09 , 3.60 (each 1H , ABq , J =10.9 Hz , H-18),
3.13(3H , s , OCH3), 3.26(6H , s , 2×OCH3), 3.30(1H ,
d , J=5.1 Hz , H-16), 3.71(3H , s , OCH3), 3.95(1H , brd ,
J=7.0 Hz , H-6), 4.33(1H , d , J=2.7 Hz , 15-OH), 4.44
(1H , dd , J =5.1 , 2.7 Hz , H-15), 4.85 (1H , d , J =4.7
Hz , 14β-H), 7.43(2H , dd , J=7.4 , 7.0 Hz), 7.52(1H , t ,
J=7.4 Hz), 7.99 (2H , d , J =7.0)(Ar-H);13 C NMR
(DEPT)(125MHz , CDCl3)δ:84.9(d , C-1), 26.6(t , C-2),
35.1(t , C-3), 39.4 (s , C-4), 48.2(d , C-5), 83.0 (d , C-
6), 44.6(d , C-7), 91.7(s , C-8), 43.9(d , C-9), 41.2(d ,
C-10), 50.0 (s , C-11), 36.4 (t , C-12), 74.0 (s , C-13),
78.8(d , C-14), 78.7(d , C-15), 89.9(d , C-16), 62.2(d ,
C-17), 80.0(t , C-18), 56.3(t , C-19), 42.8(q , N-CH3),
171.6(s , 8-OCOCH3), 21.7(q , 8-OCOCH3), 56.7(q , C-1
), 58.0(q , C-6), 61.0(q , C-16), 59.1(q , C-18), 165.3(s ,
14-OCOC6H6), 129.3(s , C-1′), 129.1(d , C-2′ 5′), 128.1(d ,
C-3′ 6′), 132.7(d , C-4′).Compound 1 was determined to be
hypaconitine by the comparison of phy sical and spectral data with
the reported data[ 6].
Compound 2　 amorphous powder , [ α] D+ 45°(c 0.50 ,
CHCl3);ESI-MS(+)m z 632 [ M + H] +.1 H NMR(400
MHz , CDCl3)δ:1.39 (3H , s , COCH3), 2.35(3H , s ,
NCH3), 3.17(3H , s , OCH3), 3.29 (6H , s , 2 ×OCH3),
3.75(3H , s , OCH3), 3.96(1H , m , H-6), 4.00(1H , m , H-
3), 4.36 (1H , d , J =2.6Hz , 15-OH), 4.46(1H , dd , J =
5.0 , 2.6 Hz , H-15), 4.89 (1H , d , J =4.8 Hz , 14β-H),
7.46(2H , dd , J=7.4 , 7.0 Hz), 7.59(1H , t , J =7.4 Hz),
8.03(2H , d , J=7.0)(Ar-H);13C NMR(DEPT)(125 MHz ,
CDCl3)δ:83.3(d , C-1), 36.0(t , C-2), 71.7(t , C-3), 43.6
(s , C-4), 46.7(d , C-5), 82.6(d , C-6), 44.4(d , C-7), 92.1
(s , C-8), 43.8(d , C-9), 41.0(d , C-10), 49.6(s , C-11),
34.4(t , C-12), 74.4(s , C-13), 79.1(d , C-14), 79.0(d , C-
15), 90.3(d , C-16), 61.2(d , C-17), 76.3(t , C-18), 50.1
(t , C-19), 42.8(q , N-CH3), 172.6(s , 8-OCOCH3), 21.6(q ,
8-OCOCH3), 56.6(q , C-1), 58.2(q , C-6), 61.2(q , C-16),
59.3(q , C-18 ), 166.3(s , 14-OCOC6H6), 130.0(s , C-1′),
129.8(d , C-2′ 5′), 128.8(d , C-3′ 6′), 133.2(d , C-4′.Com-
pound 2 was determined to be mesaconitine by the comparison of
physical and spectral data with the reported data[ 7] .
Compound 3　amorphous powder, [α] D+ 39.3°(c 0.50 ,
CHCl3);ESI-MS m z 438 [ M + H] +.1H NMR(400 MHz ,
CDCl3)δ:1.12(3H , t , N-CH2 CH3), 2.64 (1H , H-17),
3.11 , 3.62 (2H , Abq , J =8.4Hz , H-18), 3.32 (3H , s ,
OCH3), 3.35 (6H , s , 2×OCH3), 3.64 (1H , brs , H-1),
4.14(1H , d , J=6.0 , H-6), 4.18 (1H , t , J =4.4 Hz , H-
1);13C NMR(DEPT)(125 MHz , CDCl3)δ:72.4 (d , C-1),
29.6(t , C-2), 29.8(t , C-3), 38.3(s , C-4), 45.0(d , C-5),
83.4(d , C-6), 52.4(d , C-7), 74.5(s , C-8), 48.6(d , C-9),
44.3(d , C-10), 49.7(s , C-11), 30.1(t , C-12), 40.6(s , C-
13), 76.2(d , C-14), 43.0(d , C-15), 82.1(d , C-16), 63.9
(d , C-17), 80.5(t , C-18), 57.2(t , C-19), 48.5(t , N-
CH2-), 13.3(q , N-CH2-CH3), 58.1(C-6′), 56.6(C-16′),
59.4(C-18′).Compound 3 was determined to be neoline by the
comparison of physical and spectral data with the reported data[6] .
References
[ 1] 　Jiangsu New Medical College.Dict ionary of traditional Chinese ma-
terial medica , vol.1 [M] .Shanghai science and technology press ,
1988 :1577-1579.
[ 2] 　“The plant index of Anhui province” co-workers.The plant index of
Anhui province , vol.2 [ M] .Beijing China zhanwang press , 1987:
302.
[ 3] 　Wang DQ.Classification distribution and medicinal sorts of endemic
plants in Anhui province[ J] .China J Chin Mater Med , 1999 , 24
(8):451-454.
[ 4] 　Huang TK , Ding ZZ , Zhao SS , et al.Modern compendium of mate-
rial medica , Vol.2 [M] .Bei jing science and technology press of
Chinese medicine , 2001 :1792-1795.
[ 5] 　Peng CS , Wang JZ , Jian XX.Alkaloids of Aconitum racemulosum
Franch var.Pengzhouese[ J] .West China J Pharm Sci , 2000 , 15
(2):94-96.
[ 6] 　Chen HC ,Wang XK , Zhao TF , et al.Chemical constituents from
Aconitum carmichaeli[ J] .Nat Prod ResDev , 2003 , 15(4):324-
325 , 340.
[ 7] 　Ren YL , Huang ZH , Jia SS.Isolation and identificai ton of triester-
diderpenoid f rom the f lowers of Aconitum kusnezof fii Reichb [ J] .
Acta Pharm Sin , 1999 , 34(11):873-876.
黄山乌头中的二萜生物碱
赵安幸 ,彭崇胜＊ ,张晨虹 ,贾　伟
上海交通大学药学院 ,上海 200240
【摘　要】　目的:对黄山乌头中二萜生物碱类化合物进行研究。方法:应用离子交换树脂法提取黄山乌头总生物碱 ,
经色谱法分离 、纯化 , 光谱数据和理化性质确定各化合物的结构。结果:分离得到 3 个化合物 , 分别鉴定为海帕乌头碱
(Hypaconitine , 1),中乌头碱(mesaconitine , 2), 尼奥宁(Neoline , 3)。结论:3 个化合物均为首次从该植物中得到 , 双酯型乌头碱
(1 , 2)为黄山乌头主要生物碱成分。
【关键词】　黄山乌头;去甲二萜生物碱
【基金项目】　上海交通大学 PRP项目资助(No.17006)
356　　Chin J Nat Med　Sep.2007　Vol.5　No.5 　2007年 9月　第 5卷　第 5期