全 文 ：有机化学
Chinese Journal of Organic Chemistry ARTICLE

* E-mail: wfp@scu.edu.cn
Received January 9, 2014; revised January 24, 2014; published online February 14, 2014.
Project supported by the National Natural Science Foundation of China (No. 81273387).
国家自然科学基金(No. 81273387)资助项目.

Chin. J. Org. Chem. 2014, 34, 909～915 © 2014 Chinese Chemical Society & SIOC, CAS http://sioc-journal.cn/ 909

DOI: 10.6023/cjoc201401013 研究论文
黄草乌中的新的二萜生物碱
唐天兴 陈东林 王锋鹏*
(四川大学华西药学院 成都 610041)
摘要 从黄草乌(Aconitum vilmorinianum Kom.)中分离得到 20 个二萜生物碱, 并应用 HRESIMS, 1D-和 2D-NMR, 单晶
X 射线衍射等方法确定了它们的结构 . 其中一个为新的 C19 二萜生物碱 , 1-epi-16β-hydroxycardiopetaline, 它是
16β-hydroxycardiopetaline 的差向异构体; 19 个为已知化合物.
关键词 黄草乌; C19-二萜生物碱; 1-表-16β-羟基-cardiopetaline
A New C19-Diterpenoid Alkaloid from Aconitum vilmorinianum
Tang, Tianxing Chen, Donglin Wang, Fengpeng*
(West China College of Pharmacy, Sichuan University, Chengdu 610041)
Abstract A new C19-diterpenoid alkaloid, 1-epi-16β-hydroxycardiopetaline, together with 19 known diterpenoid alkaloids,
was isolated from the roots of Aconitum vilmorinianum Kom. The structure of the new alkaloid was established on the basis of
spectral data (HR-MS, X-ray crystallographic analysis, 1D- and 2D-NMR).
Keywords Aconitum vilmorinianum; C19-diterpenoid; 1-epi-16β-hydroxycardiopetaline

乌头属(Aconitum)在全世界共有 400 种左右, 广泛
的分布在北半球地区, 如亚洲、欧洲和北美洲. 而中国
特有的大约有 200 种, 其中约 76 种药用. 用途主要包括
治疗风湿性关节炎和各种疼痛等疾病 [1]. 黄草乌
(Aconitum vilmorinianum Kom.)生于海拔 2100～2500 m
间山地丛林中. 主要分布于云南中部、四川(会理)及贵
州西部. 其根有剧毒, 味麻, 可药用, 治疗跌打损伤、风
湿等症[2]. 对黄草乌中的化学成分研究早期报道较多,
从中分离得到约20余个二萜生物碱成分[1]. 由于植物的
产地、气候等因素对其化学成分影响较大, 2008 年, 谭
宁 华 等 [3] 报 道 了 从 该 植 物 中 分 离 得 到 一 个 具
C(8)-C(9)-C(10)三元环体系的新骨架的 C19-二萜生物碱.
为了更好的开发利用我国乌头属植物的药用资源, 本课
题组对其进行更深入的系统研究, 从该植物中共分离得
到 20 个化合物(Scheme 1), 其中一个为新的 C19二萜生
物碱 epi-16β-hydroxycardiopetaline (1), 其余 19 个已知
化合物分别为: talatisamine (2)[4], karakoline (3)[5], sa-
chaconitine (4)[6], 14-O-veratroylneoline (5)[7], vilmorri-
anine A (6)[8], yunaconitine (7)[9], condelphine (8)[10],
14-acetyl-sachaconitine (9)[11], indaconitine (10)[12],
14-acetylkarakoline (11)[13], 14-acetyltalatizamine (12)[14],
cammaconine (13)[15], isotalatizidine (14)[16], 8-deacetyl-
yunaconitine (15)[17], 16β-hydroxycardiopetaline (16)[18],
pseudaconine (17) [19], columbianine (18), denudatine
(19)[20], panicutine (20)[21]. 新 化 合 物 的 结 构 应 用
HRESIMS, 1D-和 2D-NMR, 单晶 X 射线衍射等方法予
以确证.
1 结果与讨论
化合物1为白色无定型粉末, 通过HR-ESI-MS确定
其分子式为 C21H33NO4 (m/z: 364.2474 [M＋H]＋, calcd
364.2487), 不饱和度为 6. 1 的 NMR 显示其含有一个氮
乙基[δH 2.25～2.32, 2.43～2.46 (m, 2H); 1.02 (t, J＝7.2
Hz, 3H); δC 46.8 (t), 11.3 (q)]和一个角甲基[δH 0.78 (s,
3H); δC 24.2 (q)]. 除氮乙基外, 该化合物仅示出 19 个碳
信号, 无甲氧基和酯基取代信号, 结合生源推测其为
C19-二萜生物碱[22,23]. 13C NMR示出该化合物有4个含氧
取代的碳信号[δC 65.4 (d), 72.4 (s), 73.9 (d), 71.2 (d)], 表
明该化合物的 4 个氧取代碳均为羟基取代. 1H NMR 示


有机化学 研究论文

910 http://sioc-journal.cn/ © 2014 Chinese Chemical Society & SIOC, CAS Chin. J. Org. Chem. 2014, 34, 909～915

N
R1
R3
R2
R4
N
R1
R3
OCH3
R5
R2
H3CO
OCH3
R4
N
R1
R3
R2
H3CO
OCH3
N
R1
R3
R2
R4
HO
H
N
HO
OH
H
H3C N
O
O
H3CCO
O
H
1 R1 = -OH, R2 = R3 = R4 = OH
3 R1 = R2 = R3 = OH, R4 = OCH3
4 R1 = R2 = OCH3, R2 = R3 = OH
9 R1 = R2 = OCH3, R2 = OH, R3 = OAc
11 R1 = R2 = OH, R3 = OAc, R4 = OCH3
16 R1 = R2 = R3 = R4 = OH
5 R1 = R2 = OH, R3 = OVr, R4 = R5 = H
6 R1 = OCH3, R2 = OAc, R3 = OAs, R4 = OH, R5 = H
7 R1 = OCH3, R2 = OAc, R3 = OAs, R4 = R5 = OH
10 R1 = OCH3, R2 = OAc, R3 = OBz, R4 = R5 = OH
15 R1 = OCH3, R2 = OH, R3 = OAs, R4 = R5 = OH
17 R1 = OCH3, R2 = R3 = R4 = R5 = OH
2 R1 = OCH3, R2 = R3 = OH
8 R1 = R2 = OH, R3 = OAc
12 R1 = OCH3, R2 = OH, R3 = OAc
14 R1 = R2 = R3 = OH
13 R1 = R4 = OCH3, R2 = R3 = OH
18 R1 = R2 = R3 = OH, R4 = OCH3
19 20
b

Scheme 1
出一个质子三重峰的信号[δH  4.52 (t, J＝4.8 Hz, 1H)]可
指定为 H-14β, 说明 C-14 位有羟基取代. HMBC 谱中,
H-14 (δH 4.52)分别与 C-8 [δC 72.4 (s)]和 C-16 [δC 71.2
(d)]相关, 表明 C-8 位和 C-16 位也为羟基取代. 剩余一
个羟基取代指定在 C-1 位是基于 HMBC 谱中 H-1 (δH
4.13)与C-3的相关(图 1). 当 1 位为 α-OH 时, C-1 化学位
移值通常为δC 72左右, 而当1位为β-OH时通常为 δC 68
左右[16], 而化合物 1 的 C-1 为 δC 65.4 (d), 可能是由于溶
剂效应影响所致. 化合物 16 以氘代吡啶为溶剂时, C-1
的化学位移同样向高场位移了约 2 ppm. 由此确证化合
物 1 为 16 的差向异构体, 命名为 1-epi-16β-hydroxycar-
diopetaline. 最后, 我们通过单晶 X 衍射分析确定了该
化合物结构(图 2), 并由 2D-NMR 归属了其所有碳氢个
信号(表 1).
N
OH
OH
OH
OH
: 1H-1H COSY
: HMBC (H C)

图 1 化合物 1 主要的 1H-1H COSY, HMBC 相关
Figure 1 The key 1H-1H COSY, HMBC correlations of 1
化合物 1 和 16 为一对差向异构体, 但两者的极性,
溶解度以及化学位移等都存在明显差异. 化合物 1 难溶
于氯仿, 而化合物16微溶于氯仿. 且两者的化学位移在
C-1, C-2, C-3, C-4, C-10, C-12 以及 C-19 都存在较大差

图 2 化合物 1 的单晶 X 衍射结构
Figure 2 X-ray structure of 1
异. 这归因于 A 环构象的不同. 对化合物 16 来说, 由于
1α-OH基与氮上的孤对电子可形成分子内氢键, 故A环
取船式构象. 反之, 而在化合物 1 中, 则无此种分子内
氢键的存在, 所以, 正如单晶 X 衍射分析示出那样, 化
合物 1 的 A 环以椅式构象存在. 该化合物其余几个环系
也通过单晶 X 衍射实验予以确证, F 环与 A 环一样为椅
式构象, D 环和 E 环同为船式构象, 七元 B 环为扭船式,
而五元 C 环为信封式.
2 结论
天然产C19-二萜生物碱的含氧取代一般都含有甲氧

Chinese Journal of Organic Chemistry ARTICLE

Chin. J. Org. Chem. 2014, 34, 909～915 © 2014 Chinese Chemical Society & SIOC, CAS http://sioc-journal.cn/ 911
表 1 化合物 1 和 16 的 NMR 数据(400 MHz for 1H NMR, 100
MHz for 13C NMR, J/Hz)
Table 1 NMR data of compounds 1 and 16 (400 MHz for 1H
NMR, 100 MHz for 13C NMR, J/Hz)
1 16 No. δH (J in Hz)a δ　 Ca δ　 Ca δ　 Cb
1
2

3

4
5
6

7
8
9
10
11
12

13
14
15

16
17
18
19
21

22
4.13 brs
1.80 hidden (α)
3.02 hidden (β)
1.39～1.43 m (β)
1.94～2.00 m (α)
—
2.00 hidden 
1.61 dd (14.4, 8.0) (α)
2.19 hidden (β)
2.22 d (7.6)
—
2.47 hidden
2.80～2.86 m
—
1.39～1.43 m (α)
2.09～2.15 m (β)
2.43 hidden
4.52 t (4.8)
2.61 dd (15.6, 4.8) (α)
2.69～2.73 m (β)
4.02 t (6.4)
2.77 brs
0.78 s
2.03, 2.41 hidden
2.25～2.32 m
2.43～2.46 m
1.02 t (7.2)
65.4 d
29.2 t

32.6 t

32.4 s
44.1 d
23.4 t

43.0 d
72.4 s
45.0 d
37.8 d
47.9 s
26.4 t

42.4 d
73.9 d
44.1 t

71.2 d
61.2 d
24.2 q
55.1 t
46.8 t

11.3 q
70.7 d
28.2 t

30.3 t

30.8 s
44.9 d
23.4 t

43.8 d
72.2 s
44.9 d
42.5 d
47.0 s
27.4 t

42.5 d
73.7 d
43.5 t

70.8 d
60.7 d
25.1 q
57.7 t
46.1 t

10.8 q
72.4 d
29.6 t

31.3 t

32.9 s
46.6 d
25.0 t

45.4 d
74.5 s
46.4 d
43.8 d
48.7 s
28.1 t

43.9 d
76.2 d
45.4 t

72.5 d
63.2 d
27.5 q
60.2 t
48.3 t

13.0 q
a In C5D5N＋CDCl3; b in CDCl3.
基, 不含甲氧基的化合物非常罕见. 另外, 该类化合物
的 C-1 的含氧取代基的构型几乎都是 α-取向, β-取向的
结构很少见. 化合物 1 是目前天然产的唯一一个无甲氧
基取代, 且 C-1 为 β-OH 取代的 C19-二萜生物碱.
3 实验部分
3.1 仪器与试剂
红外光谱用 Nicolet FT-IR 2005XV 仪测定, KBr 压
片; 质谱用 VGAutospel 3000 型和 Finigan LCQ 型质谱
仪测定; 核磁共振用 Varian UNION 400/54 核磁共振仪
测定, 溶剂CDCl3, CD3OD或C5D5N, TMS为内标; 旋光
用 Perkin Polarimeter 341 型旋光光度仪测定; 熔点用
WRX-TS 显示热差分析仪测定(未校正). 薄层层析所用
吸附剂为硅胶G, 以0.5% CMC水溶液或者0.5% NaOH,
0.5% CMC 溶液调板, 105 ℃活化 1 h 使用, 用改良的
Dragendorff试剂和20%的硫酸乙醇显色; 柱层析硅胶为
青岛海洋化工厂制品(10～40 μ). 氯仿为工业氯仿重蒸,
石油醚、丙酮、甲醇、均为分析纯, 成都化学试剂厂生
产.
3.2 植物标本
原植物 2012 年 7 月采自云南省武定县, 为种植品
种. 由中国科学院昆明植物研究所陈纪军研究员鉴定.
3.3 提取分离
黄草乌全草粉末 40 kg, 用 0.05 mol/L 的盐酸 500 L
进行渗漉至渗漉液无生物碱反应为止, 将渗漉液用浓氨
水碱化 pH 大于 10, 再用乙酸乙酯萃取. 合并乙酸乙酯
层, 减压蒸馏, 回收溶剂得到总生物碱棕色浸膏 603.5
g.
总生物碱 603.5 g, 采用丙酮和甲醇溶解, 硅胶拌
样, 干法上样, 经硅胶柱层析[硅胶 600 g, 石油醚-丙酮
(1%二乙胺), V∶V＝10∶1→1∶1]梯度洗脱. 洗脱液经
TLC 检查合并为 A～E 五部分.
A 部分(35 g)经(石油醚-丙酮, V∶V＝40∶1→20∶
1)梯度洗脱得 14-acetylsachaconitine (200 mg).
B 部分(168.7 g)部分经丙酮析晶得 talatisamine (31
g), 剩余部分经[石油醚-丙酮(1%二乙胺), V∶V＝15∶
1]洗脱得 B-1, B-2, B-3 三部分. B-1 经(氯仿-甲醇, V∶V
＝99∶1)反复柱层析得 14-acetylkarakoline (11 mg). B-2
经 [石油醚-丙酮 (1%二乙胺 ), V∶V＝9∶1]洗脱得
sachaconitine (89 mg). B-3 部分经丙酮析晶得 denudatine
(20 mg).
C 部分(135 g)经硅胶柱层析(氯仿-甲醇, V∶V＝
150∶1→99∶1)梯度洗脱得 C-1, C-2, C-3, C-4, C-5 五部
分. C-1 先经(氯仿-甲醇, V∶V＝200∶1)后用(环己烷-
丙酮, V∶V＝40∶1)洗脱得 14-acetyltalatizamine (50
mg). C-2 经[石油醚-丙酮(1%二乙胺), V∶V＝30∶1]反
复洗脱得 vilmorrianine A (813 mg), C-3 部分经[石油醚-
丙酮(1%二乙胺), V∶V＝30∶1→20∶1]梯度洗脱得
condelphine (19 mg)及C-3-2和C-3-3两部分, C-3-3经(氯
仿-甲醇, V∶V＝200∶1)洗脱得 14-o-veratroylneoline
(34 mg)和 indaconitine (11 mg). C-4 部分经反复硅胶柱
层析(石油醚-丙酮, V∶V＝20∶1)得 yunaconitine (55
mg).
D部分(59.3 g)先经丙酮析晶得karakoline (10 g), 剩
余部分经硅胶柱层析[石油醚-丙酮(1%二乙胺), V∶V＝
10∶1]洗脱得 D-1, D-2, D-3, D-4 四部分. D-1 经(氯仿-
甲醇, V∶V＝99∶1)洗脱得panicutine (42 mg). D-3经[石
油醚-丙酮(1%二乙胺), V∶V＝5∶1]洗脱得 D-3-1,
D-3-2, D-3-3, D-3-4 四部分. D-3-2 经(氯仿-甲醇, V∶
V＝98∶2)反复柱层析得 cammaconine (17 mg), D-3-3 同

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912 http://sioc-journal.cn/ © 2014 Chinese Chemical Society & SIOC, CAS Chin. J. Org. Chem. 2014, 34, 909～915
样以(氯仿-甲醇, V∶V＝98∶2)洗脱得 isotalatizidine (45
mg)和 8-deacetylyunaconitine (35 mg).
E 部分(113 g)经胶柱层析[石油醚-丙酮(1%二乙胺),
V∶V＝5∶1→1∶1]梯度洗脱得 E-1, E-2, E-3, E-4 四部
分. E-2 经[氯仿-甲醇(1%氨水), V∶V＝97∶3]反复柱层
析得 pseudaconine (21 mg), E-3 部分同样以[氯仿-甲醇
(1%氨水), V∶V＝97∶3]为展开剂洗脱得 E-3-1, E-3-2,
E-3-3 三部分. 三部分都经乙酸乙酯析晶分别得到 1 (28
mg), 16β-hydroxycardiopetaline (45 mg), columbianine
(55 mg). 化合物 1 后经吡啶溶解, 成功培养出单晶.
3.4 结构测定
1-Epi-16β-hydroxycardiopetaline (1): 白色无定型粉
末. m.p. 231～234 ℃, [α] 20D －3.3 (0.49, CH3OH); 1H
NMR (400 MHz, C5D5N＋CDCl3)和 13C NMR (100 MHz,
C5D5N＋CDCl3)见表 1; IR (KBr) ν: 3415, 1106, 1046
cm－1 ; ESI-MS m/z (%): 364 [M＋H]＋ (100); HR-ESI-MS
calcd for C21H34NO4 [M＋H]＋ 364.2487, found 364.2474.
Talatisamine (2): 白色无定型粉末. m.p. 143～144
℃; 1H NMR (400 MHz, CDCl3) δ: 1.00 (t, J＝7.2 Hz, 3H,
NCH2CH3), 3.21, 3.24, 3.29 (each s, each 3H, 3×OCH3),
4.08 (t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100 MHz,
CDCl3) δ: 86.1 (d, C-1), 25.6 (t, C-2), 32.6 (t, C-3), 38.4 (s,
C-4), 37.3 (d, C-5), 24.5 (t, C-6), 45.6 (d, C-7), 72.6 (s,
C-8), 46.7 (d, C-9), 45.5 (d, C-10), 48.4 (s, C-11), 27.5 (t,
C-12), 45.8 (d, C-13), 75.3 (d, C-14), 38.2 (t, C-15), 82.0
(d, C-16), 62.8 (d, C-17), 79.3 (t, C-18), 52.9 (t, C-19),
49.3 (t, C-21), 13.5 (q, C-22), 56.2 (q, C-1), 56.3 (q,
C-16), 56.3 (q, C-18). 以上数据与文献报道值[4]基本一
致.
Karakoline (3): 白色无定型粉末. m.p. 185～187
℃; 1H NMR (400 MHz, CDCl3) δ: 0.86 (s, 3H, H-18), 1.09
(t, J＝7.2 Hz, 3H, N-CH2CH3), 3.32 (s, 3H, OCH3), 4.20
(t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100 MHz, CDCl3) δ:
72.4 (d, C-1), 29.6 (t, C-2), 31.1 (t, C-3), 32.8 (s, C-4),
44.9 (d, C-5), 25.0 (t, C-6), 46.4 (d, C-7), 74.1 (s, C-8),
46.6 (d, C-9), 39.8 (d, C-10), 48.7 (s, C-11), 29.6 (t, C-12),
43.9 (d, C-13), 75.8 (d, C-14), 42.2 (t, C-15), 81.8 (d,
C-16), 63.3 (d, C-17), 28.2 (q, C-18), 60.1 (t, C-19), 48.3
(t, C-21), 13.0 (q, C-22), 56.2 (q, C-16). 以上数据与文献
报道值[5]基本一致.
Sachaconitine (4): 白色无定型粉末. m.p. 113～115
℃; 1H NMR (400 MHz, CDCl3) δ: 0.73 (s, 3H, H-18), 1.00
(t, J＝7.2 Hz, 3H, NCH2CH3), 3.21, 3.30 (each s, each 3H,
2×OCH3), 4.09 (dd, J＝4.8 Hz, 1H, H-14β); 13C NMR
(100 MHz, CDCl3) δ: 86.7 (d, C-1), 26.1 (t, C-2), 37.4 (t,
C-3), 34.5 (s, C-4), 50.6 (d, C-5), 25.0 (t, C-6), 45.6 (d,
C-7), 72.8 (s, C-8), 46.8 (d, C-9), 38.3 (d, C-10), 48.8 (s,
C-11), 27.6 (t, C-12), 45.6 (d, C-13), 75.5 (d, C-14), 37.7
(t, C-15), 82.1 (d, C-16), 62.5 (d, C-17), 26.1 (q, C-18),
56.7 (t, C-19), 49.3 (t, C-21), 13.6 (q, C-22), 56.2 (q, C-1),
56.3 (q, C-16). 以上数据与文献报道值[6]基本一致.
14-O-veratroylneoline (5): 白色无定型粉末 . m.p.
178～181 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.12 (t, J＝
7.2 Hz, 3H, NCH2CH3), 3.25, 3.27, 3.92, 3.93 (each s, each
3H, 4×OCH3), 4.12 (d, J＝6.4 Hz, 1H, H-6β), 5.16 (t, J＝
4.4 Hz, 1H, H-14β), 6.88～7.66 (m, 3H, aromatic protons);
13C NMR (100 MHz, CDCl3) δ: 72.0 (d, C-1), 29.6 (t,
C-2), 29.4 (t, C-3), 38.0 (s, C-4), 44.3 (d, C-5), 83.3 (d,
C-6), 53.0 (d, C-7), 74.8 (s, C-8), 45.9 (d, C-9), 43.6 (d,
C-10), 49.7 (s, C-11), 29.2 (t, C-12), 37.6 (d, C-13), 76.6
(d, C-14), 42.5 (t, C-15), 82.0 (d, C-16), 63.2 (d, C-17),
80.0 (t, C-18), 56.8 (t, C-19), 48.2 (t, C-21), 12.9 (q, C-22),
57.9 (q, C-6), 59.1 (q, C-16), 56.3 (q, C-18), 122.5 (s,
C-1), 112.0 (d, C-2), 148.5 (s, C-3), 152.9 (s, C-4), 110.3
(d, C-5), 123.3 (d, C-6), 165.7 (s, PhCO), 55.8, 55.9 (q,
aromatic OCH3). 以上数据与文献报道值[7]基本一致.
Vilmorrianine A (6): 白色无定型粉末. m.p. 180～
183 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.03 (t, J＝7.2 Hz,
3H, NCH2CH3), 3.18, 3.26, 3.30, 3.39, 3.86 (each s, each
3H, 5×OCH3), 4.10 (d, J＝6.0 Hz, 1H, H-6β), 5.03 (t, J＝
4.4 Hz, 1H, H-14β), 6.91, 8.01 (A2B2, J＝8.8 Hz, 4H,
aromatic protons); 13C NMR (100 MHz, CDCl3) δ: 82.6 (d,
C-1), 33.2 (t, C-2), 71.8 (d, C-3), 43.2 (s, C-4), 46.8 (d,
C-5), 83.4 (d, C-6), 44.7 (d, C-7), 85.8 (s, C-8), 48.7 (d,
C-9), 43.5 (d, C-10), 50.4 (s, C-11), 28.2 (t, C-12), 39.2 (d,
C-13), 75.2 (d, C-14), 38.1 (t, C-15), 82.3 (d, C-16), 61.3
(d, C-17), 77.2 (t, C-18), 48.7 (t, C-19), 47.5 (t, C-21), 13.2
(q, C-22), 55.6 (q, C-1), 57.8 (q, C-6), 56.6 (q, C-16),
59.1 (q, C-18), 169.7 (s, COCH3), 21.7 (q, COCH3), 122.8
(s, C-1), 131.6 (d, C-2 and C-6), 113.7 (d, C-3 and C-5),
163.4 (s, C-4), 165.9 (s, PhCO), 55.3 (q, aromatic OCH3).
以上数据与文献报道值[8]基本一致.
Yunaconitine (7): 白色无定型粉末. m.p. 140～143
℃; 1H NMR (400 MHz, CDCl3) δ: 1.10 (t, J＝7.2 Hz, 3H,
NCH2CH3), 3.15, 3.25, 3.29, 3.54, 3.86 (each s, each 3H,
5×OCH3), 4.02 (d, J＝6.4 Hz, 1H, H-6β), 4.86 (d, J＝4.8
Hz, 1H, H-14β), 6.91, 8.01 (A2B2, J＝8.8 Hz, 4H, aromatic
protons); 13C NMR (100 MHz, CDCl3) δ: 83.1 (d, C-1),
33.4 (t, C-2), 71.8 (d, C-3), 43.1 (s, C-4), 47.2 (d, C-5),
82.2 (d, C-6), 44.6 (d, C-7), 85.5 (s, C-8), 48.7 (d, C-9),

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40.7 (d, C-10), 50.2 (s, C-11), 35.1 (t, C-12), 74.7 (s,
C-13), 75.5 (d, C-14), 39.6 (t, C-15), 83.5 (d, C-16), 61.7
(d, C-17), 77.2 (t, C-18), 48.7 (t, C-19), 47.5 (t, C-21), 13.2
(q, C-22), 55.8 (q, C-1), 58.8 (q, C-6), 57.7 (q, C-16),
59.1 (q, C-18), 169.7 (s, COCH3), 21.7 (q, COCH3), 122.6
(s, C-1), 131.6 (d, C-2 and C-6), 113.7 (d, C-3 and C-5),
163.4 (s, C-4), 165.9 (s, PhCO), 55.3 (q, aromatic OCH3).
以上数据与文献报道值[9]基本一致.
Condelphine (8): 白色无定型粉末. m.p. 158～159
℃; 1H NMR (400 MHz, CDCl3) δ: 1.12 (t, J＝7.2 Hz, 3H,
N-CH2CH3), 3.29, 3.36 (each s, each 3H, 2×OCH3), 4.86
(t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100 MHz, CDCl3) δ:
72.0 (d, C-1), 29.0 (t, C-2), 29.6 (t, C-3), 37.1 (s, C-4),
41.2 (d, C-5), 24.9 (t, C-6), 45.3 (d, C-7), 74.7 (s, C-8),
44.6 (d, C-9), 36.4 (d, C-10), 48.8 (s, C-11), 26.5 (t, C-12),
43.1 (d, C-13), 76.6 (d, C-14), 42.5 (t, C-15), 81.9 (d,
C-16), 63.6 (d, C-17), 78.8 (t, C-18), 56.0 (t, C-19), 48.4 (t,
C-21), 12.9 (q, C-22), 56.4 (q, C-16), 59.4 (q, C-18),
170.4 (s, COCH3), 21.3 (q, COCH3). 以上数据与文献报
道值[10]基本一致.
14-Acetylsachaconitine (9): 白色无定型粉末. m.p.
87～91 ℃; 1H NMR (400 MHz, CDCl3) δ: 0.74 (3H, s,
H-18), 1.02 (t, J＝7.2 Hz, 3H, NCH2CH3), 3.19, 3.24 (each
3H, s, 2×OCH3), 4.79 (t, J＝4.8 Hz, 1H, H-14β). 与标准
品[石油醚-丙酮, V∶V＝5∶1; 氯仿-甲醇, V∶ V＝
98∶2] Rf 值相同, 以上氢谱数据与文献值[11]基本一致.
Indaconitine (10): 白色无定型粉末. m.p. 189～193
℃; 1H NMR (400 MHz, CDCl3) δ: 1.09 (t, J＝7.2 Hz, 3H,
N-CH2CH3), 3.14, 3.24, 3.28, 3.53 (each s, each 3H, 4×
OCH3), 4.02 (d, J＝6.4 Hz, 1H, H-6β), 4.89 (d, J＝4.4 Hz,
1H, H-14β), 7.41～8.06 (m, 5H, aromatic protons); 13C
NMR (100 MHz, CDCl3) δ: 83.4 (d, C-1), 35.1 (t, C-2),
71.6 (d, C-3), 43.1 (s, C-4), 48.6 (d, C-5), 82.2 (d, C-6),
44.5 (d, C-7), 85.5 (s, C-8), 47.2 (d, C-9), 40.7 (d, C-10),
50.2 (s, C-11), 33.4 (t, C-12), 74.6 (s, C-13), 78.7 (d,
C-14), 39.5 (t, C-15), 83.0 (d, C-16), 61.7 (d, C-17), 77.0
(t, C-18), 48.8 (t, C-19), 47.4 (t, C-21), 13.2 (q, C-22), 55.8
(q, C-1), 58.7 (q, C-6), 57.8 (q, C-16), 59.1 (q, C-18),
169.8 (s, COCH3), 21.5 (q, COCH3), 130.0 (s, C-1), 128.5
(d, C-2 and C-6), 129.6 (d, C-3 and C-5), 133.1 (d, C-4),
165.9 (s, PhCO). 以上数据与文献报道值[12]基本一致.
14-Acetylkarakoline (11): 白色无定型粉末 . m.p.
99～100 ℃; 1H NMR (400 MHz, CDCl3) δ: 0.89 (s, 3H,
H-18), 1.12 (t, J＝7.2 Hz, 3H, N-CH2CH3), 3.27 (s, 3H,
OCH3), 4.86 (t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100
MHz, CDCl3) δ: 72.1 (d, C-1), 29.4 (t, C-2), 30.8 (t, C-3),
32.7 (s, C-4), 45.3 (d, C-5), 25.2 (t, C-6), 44.6 (d, C-7),
74.8 (s, C-8), 46.1 (d, C-9), 36.6 (d, C-10), 48.3 (s, C-11),
29.0 (t, C-12), 43.1 (d, C-13), 77.1 (d, C-14), 42.5 (t,
C-15), 82.0 (d, C-16), 63.0 (d, C-17), 27.5 (q, C-18), 60.2
(t, C-19), 48.3 (t, C-21), 12.9 (q, C-22), 56.0 (q, C-16),
170.5 (s, COCH3), 21.3 (q, COCH3). 以上数据与文献报
道值[13]基本一致.
14-Acetyltalatizamine (12): 白色无定型粉末. m.p.
95～97 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.05 (t, J＝7.2
Hz, 3H, NCH2CH3), 3.22, 3.27, 3.29 (each s, each 3H, 3×
OCH3), 4.81 (t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100
MHz, CDCl3) δ: 85.7 (d, C-1), 26.1 (t, C-2), 32.6 (t, C-3),
38.4 (s, C-4), 35.2 (d, C-5), 24.8 (t, C-6), 45.8 (d C-7),
73.6 (s, C-8), 46.1 (d, C-9), 44.8 (d, C-10), 48.6 (s, C-11),
28.3 (t, C-12), 45.3 (d, C-13), 76.6 (d, C-14), 40.8 (t,
C-15), 81.5 (d, C-16), 62.2 (d, C-17), 79.4 (t, C-18), 53.0
(t, C-19), 49.3 (t, C-21), 13.5 (q, C-22), 56.1 (q, C-1), 56.2
(q, C-16), 59.4 (q, C-18), 170.7 (s, COCH3), 21.3 (q,
COCH3). 以上数据与文献报道值[14]基本一致.
Cammaconine (13): 白色无定型粉末. m.p. 136～
137 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.06 (t, J＝7.2 Hz,
3H, NCH2CH3), 3.27, 3.34 (each s, each 3H, 2×OCH3),
4.14 (t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100 MHz,
CDCl3) δ: 86.2 (d, C-1), 25.6 (t, C-2), 32.0 (t, C-3), 39.0 (s,
C-4), 45.8 (d, C-5), 24.5 (t, C-6), 45.7 (d, C-7), 72.8 (s,
C-8), 46.8 (d, C-9), 37.5 (d, C-10), 48.7 (s, C-11), 27.6 (t,
C-12), 45.4 (d, C-13), 75.5 (d, C-14), 38.2 (t, C-15), 82.1
(d, C-16), 62.9 (d, C-17), 68.7 (t, C-18), 52.9 (t, C-19),
49.5 (t, C-21), 13.6 (q, C-22), 56.5 (q, C-1), 56.3 (q,
C-16). 以上数据与文献报道值[15]基本一致.
Isotalatizidine (14): 白色无定型粉末. m.p. 116～
117 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.17 (t, J＝7.2 Hz,
3H, NCH2CH3), 3.31, 3.34 (each s, each 3H, 2×OCH3),
4.20 (t, J＝4.8 Hz, 1H, H-14β); 13C NMR (100 MHz,
CDCl3) δ: 72.1 (d, C-1), 26.7 (t, C-2), 29.6 (t, C-3), 37.1 (s,
C-4), 41.7 (d, C-5), 24.7 (t, C-6), 45.0 (d, C-7), 74.0 (s,
C-8), 46.6 (d, C-9), 43.9 (d, C-10), 48.5 (s, C-11), 28.3 (t,
C-12), 39.8 (d, C-13), 75.6 (d, C-14), 41.7 (t, C-15), 81.8
(d, C-16), 64.0 (d, C-17), 78.9 (t, C-18), 56.5 (t, C-19),
48.5 (t, C-21), 13.0 (q, C-22), 56.3 (q, C-16), 59.4 (q,
C-18). 以上数据与文献报道值[16]基本一致.
8-Deacetylyunaconitine (15): 白色无定型粉末. m.p.
101～104 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.12 (t, J＝
7.2 Hz, 3H, NCH2CH3), 3.25, 3.28, 3.31, 3.41, 3.86 (each

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914 http://sioc-journal.cn/ © 2014 Chinese Chemical Society & SIOC, CAS Chin. J. Org. Chem. 2014, 34, 909～915
s, each 3H, 5×OCH3), 4.07 (d, J＝6.8 Hz, 1H, H-6β), 5.12
(d, J＝4.8 Hz, 1H, H-14β), 6.92, 7.98 (A2B2, J＝8.8 Hz,
4H). 与标准品(石油醚-丙酮, V∶V＝3 1∶ ; 氯仿-甲醇,
V∶V＝97 3∶ ) Rf 值相同, 以上氢谱数据与文献值[17]基
本一致.
16β-Hydroxycardiopetaline (16): 白色无定型粉末.
m.p. 213～216 ℃; 1H NMR (400 MHz, CDCl3) δ: 0.88 (s,
3H, H-18), 1.11 (t, J＝7.2 Hz, 3H, NCH2CH3), 4.32 (t, J＝
4.8 Hz, 1H, H-14β); 13C NMR 谱数据见表 1. 以上数据与
文献报道值[18]基本一致.
Pseudaconine (17): 白色无定型粉末. m.p. 205～
208 ℃; 1H NMR (400 MHz, CDCl3) δ: 1.10 (t, J＝7.2 Hz,
3H, NCH2CH3), 3.23, 3.30, 3.31, 3.41 (each s, each 3H,
4×OCH3), 4.14 (d, J＝7.2 Hz, 1H, H-6β), 3.98 (d, J＝4.8
Hz, 1H, H-14β); 13C NMR (100 MHz, CDCl3) δ: 84.3 (d,
C-1), 35.6 (t, C-2), 72.1 (d, C-3), 43.4 (s, C-4), 48.5 (d,
C-5), 82.1 (d, C-6), 52.0 (d, C-7), 72.6 (s, C-8), 50.2 (d,
C-9), 41.8 (d, C-10), 50.0 (s, C-11), 33.7 (t, C-12), 76.6 (s,
C-13), 79.4 (d, C-14), 39.8 (t, C-15), 82.9 (d, C-16), 62.2
(d, C-17), 77.3 (t, C-18), 49.1 (t, C-19), 47.2 (t, C-21), 13.6
(q, C-22), 56.1 (q, C-1), 57.2 (q, C-6), 57.7 (q, C-16),
59.2 (q, C-18). 以上数据与文献报道值[19]基本一致.
Columbianine (18): 白色无定型粉末. m.p. 202～
205 ℃; 1H NMR (400 MHz, CD3OD) δ: 1.12 (t, J＝7.2
Hz, 3H, NCH2CH3), 3.33 (s, 3H, OCH3), 4.13 (t, J＝4.8
Hz, 1H, H-14β); 13C NMR (100 MHz, CD3OD) δ: 73.8 (d,
C-1), 25.7 (t, C-2), 27.0 (t, C-3), 38.9 (s, C-4), 45.2 (d,
C-5), 30.4 (t, C-6), 42.1 (d, C-7), 75.7 (s, C-8), 47.3 (d,
C-9), 46.8 (d, C-10), 49.8 (s, C-11), 31.0 (t, C-12), 41.7 (d,
C-13), 76.4 (d, C-14), 42.7 (t, C-15), 84.4 (d, C-16), 64.6
(d, C-17), 68.1 (t, C-18), 57.6 (t, C-19), 49.2 (t, C-21), 13.3
(q, C-22), 56.4 (q, C-16). 经单晶X射线衍射实验确定了
其结构.
Denudatine (19): 白色无定型粉末. m.p. 249～251
℃; 1H NMR (400 MHz, CDCl3) δ: 1.12 (t, J＝7.2 Hz, 3H,
NCH2CH3), 0.70 (s, 3H, H-18), 4.29 (brs, H-15, 1H), 5.25,
5.04 (each s, each 1H, H-17). 与标准品(石油醚-丙酮,
V∶V＝5∶1; 氯仿-甲醇, V∶V＝98∶2) Rf 值相同, 以
上氢谱数据与文献值[20]基本一致.
Panicutine (20): 白色无定型粉末. m.p. 211～214
℃; 1H NMR (400 MHz, CDCl3) δ: 1.47 (s, 3H, H-18), 2.35
(s, 3H, NCH3), 4.81, 4.97 (each s, each 1H, H2-17); 13C
NMR (100 MHz, CDCl3) δ: 35.7 (t, C-1), 70.7 (d, C-2),
43.7 (t, C-3), 36.7 (s, C-4), 62.9 (d, C-5), 203.7 (s, C-6),
50.2 (t, C-7), 41.6 (s, C-8), 59.0 (d, C-9), 44.3 (s, C-10),
211.7 (s, C-11), 52.6 (d, C-12), 22.5 (t, C-13), 49.8 (d,
C-14), 29.1 (t, C-15), 142.0 (s, C-16), 110.5 (t, C-17), 31.0
(q, C-18), 60.2 (t, C-19), 68.3 (d, C-20), 43.2 (q, C-21),
169.9 (s, COCH3), 21.5 (q, COCH3), 以上数据与文献报
道值[21]基本一致.
3.5 1-Epi-16β-hydroxycardiopetaline 的单晶 X 衍射
测定
在吡啶中室温培养 2 周, 得到块状单晶. 晶体大小
为 0.3 mm×0.3 mm×0.2 mm, 斜方晶系, 空间群为
P212121, a＝7.9517(4) Å, b＝12.7354(5) Å, c＝17.9181(8)
Å, V＝1814.54(14) Å3, Dc＝1.331 mg/mm3, λ＝0.7107
nm, μ＝0.091 mm－1, F(000)＝792, T＝293.15 K, 收集衍
射点数为 4922, 独立衍射点数 3252, 优化方法基于 F2
全矩阵最小二乘法, 衍射区为－6≤h≤9, －15≤k≤14,
－22≤l≤21, 最后修正值 R1为 0.0471, R(all)为 0.0552.
1-epi-16β-hydroxycardiopetaline 的 X 射线衍射数据存放
于英国剑桥X单晶衍射数据中心, CCDC编号为978786.
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