全 文 ：中草药 Chinese Traditional and Herbal Drugs 第 44 卷 第 11 期 2013 年 6 月

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云南红豆杉种子的化学成分研究
刘丽华 1，王丽军 2，任天坤 3，史清文 3，张嫚丽 3*
1. 天津中新药业集团股份有限公司第六中药厂，天津 300401
2. 唐山市中医院 药剂科，河北 唐山 063000
3. 河北医科大学药学院 天然药物化学教研室，河北 石家庄 050017
摘 要：目的 研究云南红豆杉 Taxus yunnanensis 种子的化学成分。方法 通过色谱技术进行分离纯化，利用核磁共振技术
鉴定化合物的结构。结果 从云南红豆杉种子中分离得到 12 个紫杉烷类化合物，分别鉴定为 7-表-10-去乙酰基紫杉醇（1）、
9α, 10β-二乙酰基-2α-羟基-5α-桂皮酰基-3, 11-环化紫杉烷-4(20)-烯-13-酮（2）、2α, 7α, 10β-三乙酰基-9α-羟基-5α-桂皮酰基-3,
11-环化紫杉烷-4(20)-烯-13-酮（3）、2α-乙酰基-9α, 10β-二羟基-5α-桂皮酰基紫杉烷-4(20), 11-二烯-13-酮（4）、2α, 7β, 9α, 10β-
四乙酰基-5α-桂皮酰基-11, 12-环氧紫杉烷-4(20)-烯-13-酮（5）、7β, 9α, 10β-三乙酰基-5α-桂皮酰基紫杉烷-4(20), 11-烯-13α-醇
（6）、9-去乙酰基紫杉宁 A（7）、5α-去桂皮酰基紫杉欧吉酚（8）、2α, 5α, 10β, 13α-四乙酰基-1β, 7β, 9α-三羟基-4, 20-环氧紫杉
烷-11-烯（9）、7β, 9α, 10β-三乙酰基-2α, 5α, 13α-三羟基紫杉烷-4(20), 11-二烯（10）、7, 9, 10, 13-tetra-O-deacetylabeobaccatin VI
（11）、taxacustin（12）。结论 化合物 2、3、7～12 为首次从该植物中分离得到。
关键词：云南红豆杉；紫杉烷；9α, 10β-二乙酰基-2α-羟基-5α-桂皮酰基-3, 11-环化紫杉烷-4(20)-烯-13-酮；9-去乙酰基紫杉宁
A；5α-去桂皮酰基紫杉欧吉酚
中图分类号：R284.1 文献标志码：A 文章编号：0253-2670(2013)11- 1380 - 06
DOI: 10.7501/j.issn.0253-2670.2013.11.004
Chemical constituents from seeds of Taxus yunnanensis
LIU Li-hua1, WANG Li-jun2, REN Tian-kun3, SHI Qing-wen3, ZHANG Man-li3
1. Tianjin Sixth Chinese Medicine Factory, Zhongxin Pharmaceutical Co., Ltd., Tianjin 300401, China
2. Department of Pharmacy, Tangshan Hospital of Traditional Chinese Medicine, Tangshan 063000, China
3. Department of Natural Product Chemistry, School of Pharmaceutical Sciences, Hebei Medical University, Shijiazhuang
050017, China
Abstract: Objective To study the chemical constituents from the seeds of Taxus yunnanensis. Methods The chemical constituents
in the seeds of T. yunnanensis were isolated by chromatography and identified by a comprehensive analysis on the spectral data.
Results Twelve taxanes were isolated from the seeds of T. yunnanensis and identified as 7-epi-10-deacetyltaxol (1), 2-
deacetoxytaxuspine C (2), 9α-hydroxy-2α, 7α, 10β-triacetoxy-5α-cinnamoyloxy-3, 11-cyclotaxa-4(20)-en-13-one (3), 2α-acetoxy-
5α-cinnamoyloxy-9α, 10β-dihydroxy-taxa-4 (20), 11-diene-13-one (4), dantaxusin C (5), taxezopidine H (6), 9-deacetyltaxinine A (7),
5α-decinnamoyltaxagifine (8), taxumairol B (9), 2α, 5α, 13α-trihydroxy-7β, 9α, 10β-triacetoxy-taxa-4(20), 11-diene (10), 7, 9, 10,
13-tetra-O-deacetylabeobaccatin VI (11), and taxacustin (12). Conclusion Compounds 2, 3, and 7—12 are isolated from T.
yunnanensis for the first time.
Key words: Taxus yunnanensis W. C. Cheng & L. K. Fu; taxanes; 2-deacetoxytaxuspine C; 9-deacetyltaxinine A; 5α-decinnamoyltaxagifine

紫杉醇以其独特的抗肿瘤作用机制和对卵巢
癌、乳腺癌、Kaposi’s 综合征的神奇疗效，一直是全
世界药物工作者的研究热点。由于紫杉醇在树皮中
的量极低，药源供应紧缺，研究者们对红豆杉属的
其他种植物进行了大量的研究，希望从中发现新的
紫杉醇类似物，或找到紫杉醇的生物合成前体，从
而扩大紫杉醇的药源或寻找开发出新的紫杉烷类
抗癌活性成分。尽管文献报道紫杉烷类化合物

收稿日期：2013-03-26
作者简介：刘丽华（1964—），女，河北昌黎人，高级工程师，学士，主要从事中药分析和药物新品研发工作。
Tel: (022)26950844 13752350077 E-mail: tjlzyliu@163.com
*通信作者 张嫚丽（1978—），女，副教授，博士，主要从事天然产物活性成分研究。Tel: (0311)86265634 E-mail: zhang-manli@163.com
中草药 Chinese Traditional and Herbal Drugs 第 44 卷 第 11 期 2013 年 6 月

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已达到 560 多个[1]，但是新的紫杉烷类化合物仍然
不断地被发现[2-3]。云南红豆杉 Taxus yunnanensis W.
C. Cheng & L. K. Fu 主要分布在云南省保山市、腾
冲县，滇西北的大理、中甸、丽江、维西一带，是
我国生产紫杉醇的主要树种。目前对其化学成分研
究主要涉及到树皮、心材、枝和叶，对种子化学成
分的研究还未见报道。本课题组长期进行紫杉烷
类化学成分研究，从云南红豆杉种子中分离得到
12 个紫杉烷类化合物，分别鉴定为 7-表-10-去乙
酰基紫杉醇（7-epi-10-deacetyltaxol，1）、9α, 10β-
二乙酰基-2α-羟基-5α-桂皮酰基-3, 11-环化紫杉烷-
4(20)-烯-13-酮（2-deacetoxytaxuspine C，2）、2α, 7α,
10β-三乙酰基-9α-羟基-5α-桂皮酰基-3, 11-环化紫
杉烷 -4(20)-烯 -13-酮 [9α-hydroxy-2α, 7α, 10β-
triacetoxy-5α-cinnamoyloxy-3, 11-cyclotaxa-4(20)-
en-13-one，3]、2α-乙酰基-9α, 10β-二羟基-5α-桂皮
酰基紫杉烷-4(20), 11-二烯-13-酮 [2α-acetoxy-5α-
cinnamoyloxy-9α, 10β-dihydroxy-taxa-4(20), 11-diene-
13-one，4]、2α, 7β, 9α, 10β-四乙酰基-5α-桂皮酰
基-11, 12-环氧紫杉烷-4(20)-烯-13-酮（dantaxusin
C，5）、7β, 9α, 10β-三乙酰基-5α-桂皮酰基紫杉烷-
4(20), 11-烯-13α-醇（taxezopidine H，6）、9-去乙
酰基紫杉宁 A（9-deacetyltaxinine A，7）、5α-去桂
皮酰基紫杉欧吉酚（5α-decinnamoyltaxagifine，8）、
2α, 5α, 10β, 13α-四乙酰基-1β, 7β, 9α-三羟基-4,
20-环氧紫杉烷-11-烯（taxumairol B，9）、7β, 9α,
10β-三乙酰基-2α, 5α, 13α-三羟基紫杉烷-4(20),
11-二烯 [2α, 5α, 13α-trihydroxy-7β, 9α, 10β-triacetoxy-
taxa-4(20), 11-diene ， 10]、 7, 9, 10, 13-tetra-O-
deacetylabeobaccatin VI（11）、taxacustin（12）。其中
化合物 2、3、7～12 为首次从该植物中分离得到。
1 仪器与材料
Bruker Advance—500 核磁共振仪测定（瑞士布
鲁克公司）；薄层色谱和柱色谱用硅胶均为青岛海洋
化工厂生产。薄层显色剂为 10% H2SO4 乙醇溶液，
喷雾后加热显色。
药材于 2009 年采自云南保山，经河北医科大学
王建华教授鉴定为云南红豆杉 Taxus yunnanensis W.
C. Cheng & L. K. Fu 的种子。样品（2009-10）现保
存于河北医科大学药学院生药标本室。
2 提取与分离
取粉碎后种子约 2.2 kg，用 95%乙醇冷浸提取，
每次浸泡时间为 7 d，共提取 3 次。合并提取液浓缩
得浸膏约 120 g。将浸膏分散于蒸馏水中并加入适量
的 NaCl 使达饱和，石油醚脱脂后，醋酸乙酯萃取 3
次，所得醋酸乙酯萃取液分别用 5% HCl 水溶液和
5% Na2CO3水溶液萃取处理后，得到云南红豆杉种
子的碱性部位约 2.2 g、酚性部位约 2.4 g 及中性部
位约 52 g。碱性部位采用硅胶柱色谱法进行分离，
二氯甲烷-甲醇（9∶1）洗脱，收集流出液，薄层检
识合并后，得到 15 个流分 Fr. 1～15。Fr. 11 中析出
白色粉末状固体，为化合物 1（10 mg）。中性部位
采用硅胶柱色谱法进行分离，石油醚-醋酸乙酯（9∶
1、8∶2、7∶3、6∶4、1∶1、2∶3）梯度洗脱，收
集各流出液，薄层检识合并后，得到 15 个流分 Fr.
1～15。其中 Fr. 1 析出白色固体，经丙酮重结晶后
得到化合物 2（12 mg）。中性部位 Fr. 2 浓缩过程中
析出白色固体，经丙酮重结晶后得到化合物 3（8
mg）。浓缩后采用硅胶柱色谱进行分离，石油醚-醋
酸乙酯（9∶1、8∶2、7∶3）梯度洗脱，得到化合
物 4（12 mg）和 5（10 mg）；中性部位 Fr. 2 母液进
行柱色谱分离得到 Fr. 2-2～2-5，再经制备高效液相
色谱分离，流动相为乙腈-水（60∶40），得到化合
物 6（7 mg）。中性部位 Fr. 4～6 合并后采用硅胶柱
色谱进行分离，二氯甲烷-丙酮（8∶2、7∶3、6∶4）
梯度洗脱，薄层检识合并，共得到 14 个流分，分别
经 Sephadex LH-20 色谱，甲醇洗脱纯化后，得化合
物 7（15 mg）、8（12 mg）和 9（10 mg）。中性部
位 Fr. 10 硅胶柱色谱进行分离，二氯甲烷-丙酮（8∶
2、7∶3、1∶1）梯度洗脱，共得到 10 个流分。分
别经 Sephadex LH-20 色谱，甲醇洗脱纯化后，得化
合物 10（15 mg）、11（12 mg）和 12（10 mg）。
3 结构鉴定
化合物 1：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 5.73 (1H, d, J = 7.4 Hz, H-2),
3.91 (1H, d, J = 7.4 Hz, H-3), 4.90 (1H, dd, J = 9.0,
3.9 Hz, H-5), 2.32 (2H, m, H-6a, 6b), 3.66 (1H, brdd,
J = 12.2, 4.8 Hz, H-7), 4.73 (1H, s, 7-OH), 5.42 (1H,
s, H-10), 4.11 (1H, s, 10-OH), 6.23 (1H, m, H-13),
2.38 (1H, m, H-14a), 2.22 (1H, m, H-14b), 1.20 (3H,
s, H-16), 1.08 (3H, s, H-17), 1.74 (3H, s, H-18), 1.72
(3H, s, H-19), 4.39 (2H, s, H-20), 8.16 (2H, d, J = 7.7
Hz, Bz-H-2′, 6′), 7.52 (2H, t, J = 7.9 Hz, Bz-H-3′, 5′),
7.61 (1H, t, J = 7.5 Hz, Bz-H-4′), 4.79 (1H, brs, H-2′),
3.44 (1H, brs, 2′-OH), 5.79 (1H, dd, J = 9.2, 2.7 Hz,
H-3′), 7.37～7.72 (5H, m, Ar-H-1′′~5′′)；13C-NMR
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(125 MHz, CDCl3) δ: 79.1 (C-1), 75.4 (C-2), 40.3
(C-3), 81.9 (C-4), 82.6 (C-5), 35.4 (C-6), 75.8 (C-7),
57.1 (C-8), 214.9 (C-9), 77.7 (C-10), 135.5 (C-11),
137.7 (C-12), 72.5 (C-13), 36.3 (C-14), 42.4 (C-15),
26.0 (C-16), 20.5 (C-17), 14.3 (C-18), 16.6 (C-19),
77.7 (C-20), 22.5, 172.3 (OCOCH3), 166.9 (Ar-CO),
126.5～128.6 (Ar-C), 73.1 (C-2′), 54.9 (C-3′), 166.9
(5′-CO)。以上数据与文献报道一致[4]，故鉴定化合
物 1 为 7-表-10-去乙酰基紫杉醇。
化合物 2：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 2.01 (1H, m, H-1), 5.15 (1H, d,
J = 4.9 Hz, H-2), 5.61 (1H, m, H-5), 2.19 (1H, m,
H-6a), 1.77 (1H, m, H-6b), 1.78 (1H, m, H-7a), 1.28
(1H, m, H-7b), 5.69 (1H, d, J = 9.7 Hz, H-9), 5.62
(1H, d, J = 9.7 Hz, H-10), 3.50 (1H, q, J = 7.2 Hz,
H-12), 2.79 (1H, d, J = 20.6 Hz, H-14a), 2.50 (1H, dd,
J = 20.6, 7.7 Hz, H-14b), 1.20 (3H, s, 16-CH3), 1.60
(3H, s, 17-CH3), 1.27 (3H, s, 18-CH3), 1.40 (3H, s,
19-CH3), 5.89 (1H, s, H-20a), 5.68 (1H, s, H-20b),
2.05, 2.04 (各 3H, s, 2×OCOCH3), 6.39 (1H, d, J =
16.1 Hz, H-2′), 7.67 (1H, d, J = 16.1 Hz, H-3′), 7.55
(2H, m, H-5′, 9′), 7.37 (3H, m, H-6′～8′)；13C-NMR
(125 MHz, CDCl3) δ: 50.6 (C-1), 75.7 (C-2), 66.4
(C-3), 142.9 (C-4), 76.1 (C-5), 25.6 (C-6), 31.0 (C-7),
44.4 (C-8), 82.1 (C-9), 79.4 (C-10), 58.4 (C-11), 51.8
(C-12), 215.3 (C-13), 38.2 (C-14), 42.7 (C-15), 26.6
(C-16), 29.0 (C-17), 15.5 (C-18), 25.6 (C-19), 127.9
(C-20), 166.0 (C-1′), 117.7 (C-2′), 145.3 (C-3′), 134.5
(C-4′), 128.1 (C-5′, 9′), 128.7 (C-6′, 8′), 130.1 (C-7′),
21.0 (9, 10-OCOCH3), 169.8, 171.0 (9, 10-OCOCH3)。以
上数据与文献报道一致[5]，故鉴定化合物 2 为 9α,
10β-二乙酰基-2α-羟基-5α-桂皮酰基-3, 11-环化紫杉
烷-4(20)-烯-13-酮。
化合物 3：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 2.15 (1H, m, H-1), 6.05 (1H, d,
J = 5.5 Hz, H-2), 5.71 (1H, t, J = 9.8 Hz, H-5), 2.67
(1H, ddd, J = 15.2, 10.4, 4.6 Hz, H-6a), 2.01 (1H, ddd,
J = 15.2, 8.8, 1.5 Hz, H-6b), 5.32 (1H, dd, J = 4.6, 1.5
Hz, H-7b), 4.52 (1H, dd, J = 9.4, 2.5 Hz, H-9), 3.29
(1H, d, J = 2.5 Hz, 9-OH), 5.34 (1H, d, J = 9.4 Hz,
H-10), 3.62 (1H, q, J = 7.7 Hz, H-12), 2.62 (1H, d, J =
20.5 Hz, H-14a), 2.52 (1H, dd, J = 20.5, 6.8 Hz,
H-14b), 1.24 (3H, s, 16-CH3), 1.55 (3H, s, 17-CH3),
1.33 (3H, s, 18-CH3), 1.42 (3H, s, 19-CH3), 5.84 (1H,
s, H-20a), 5.70 (1H, s, H-20b), 2.16 (3H, s, -OCOCH3),
2.08 (3H, s, -OCOCH3), 1.95 (3H, s, -OCOCH3), 6.34
(1H, d, J = 16.0 Hz, H-2′), 7.66 (1H, d, J = 16.0 Hz,
H-3′), 7.54 (2H, m, H-5′, 9′), 7.38 (3H, m, H-6′～8′)；
13C-NMR (125 MHz, CDCl3) δ: 48.2 (C-1), 75.9
(C-2), 65.7 (C-3), 141.6 (C-4), 74.0 (C-5), 30.8 (C-6),
73.5 (C-7), 48.7 (C-8), 83.6 (C-9), 84.8 (C-10), 58.1
(C-11), 52.5 (C-12), 214.2 (C-13), 38.8 (C-14), 42.9
(C-15), 27.0 (C-16), 28.9 (C-17), 15.9 (C-18), 24.8
(C-19), 128.4 (C-20), 165.3 (C-1′), 117.5 (C-2′), 145.2
(C-3′), 134.1 (C-4′), 128.2 (C-5′, 9′), 128.9 (C-6′, 8′),
130.3 (C-7′), 21.3, 21.3, 20.9 (2, 7, 10-OCOCH3),
169.2, 169.7, 172.6 (2, 7, 10-OCOCH3)。以上数据与
文献报道一致[6]，故鉴定化合物 3 为 2α, 7α, 10β-三
乙酰基-9α-羟基-5α-桂皮酰基-3, 11-环化紫杉烷-
4(20)-烯-13-酮。
化合物 4：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 2.14 (1H, m, H-1), 5.51 (1H, dd,
J = 6.2, 1.8 Hz, H-2), 3.36 (1H, d, J = 6.2 Hz, H-3),
5.32 (1H, t, J = 2.7 Hz, H-5), 1.97 (1H, m, H-6a), 1.74
(1H, m, H-6b), 1.79 (1H, m, H-7a), 1.50 (1H, m,
H-7b), 1.18 (1H, d, J = 9.1 Hz, H-9), 4.89 (1H, d, J =
9.1 Hz, H-10), 2.83 (1H, dd, J = 20.0, 7.0 Hz, H-14a),
2.42 (1H, d, J = 20.0 Hz, H-14b), 1.22 (3H, s,
16-CH3), 1.70 (3H, s, 17-CH3), 2.16 (3H, s, 18-CH3),
1.10 (3H, s, 19-CH3), 5.31 (1H, s, H-20a), 4.84 (1H, s,
H-20b), 2.06 (3H, s, 2-OCOCH3), 6.43 (1H, d, J =
16.0 Hz, H-2′), 7.64 (1H, d, J = 16.0 Hz, H-3′), 7.75
(2H, d, J = 7.5 Hz, H-5′, 9′), 7.44 (1H, t, J = 7.5 Hz,
H-6′, 8′), 7.39 (1H, m, H-7′)；13C-NMR (125 MHz,
CDCl3) δ: 48.8 (C-1), 69.6 (C-2), 43.0 (C-3), 142.8
(C-4), 78.5 (C-5), 28.3 (C-6), 26.2 (C-7), 44.7 (C-8),
77.6 (C-9), 73.2 (C-10), 155.5 (C-11), 136.2 (C-12),
200.0 (C-13), 36.1 (C-14), 38.7 (C-15), 37.4 (C-16),
25.1 (C-17), 13.9 (C-18), 17.6 (C-19), 116.4 (C-20),
166.6 (C-1′), 117.8 (C-2′), 145.4 (C-3′), 134.7 (C-4′),
128.2 (C-5′, 9′), 128.7 (C-6′, 8′), 130.3 (C-7′), 21.4,
170.0 (OCOCH3)。以上数据与文献报道一致[7]，故
鉴定化合物 4 为 2α-乙酰基-9α, 10β-二羟基-5α-桂皮
酰基紫杉烷-4(20), 11-二烯-13-酮。
化合物 5：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 1.98 (1H, dd, J =8.6, 1.8 Hz,
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H-1), 5.77 (1H, dd, J =6.0, 1.8 Hz, H-2), 3.07 (1H, d,
J = 6.0 Hz, H-3), 5.52 (1H, dd, J =2.0, 3.9 Hz, H-5),
2.14 (1H, m, H-6a), 1.84 (1H, m, H-6b), 5.64 (1H, dd,
J = 11.5, 5.6 Hz, H-7), 6.02 (1H, d, J = 11.0 Hz, H-9),
5.46 (1H, d, J = 11.0 Hz, H-10), 2.68 (1H, dd, J =
20.2, 8.6 Hz, H-14a), 2.34 (1H, d, J = 20.2 Hz,
H-14b), 0.82 (3H, s, 16-CH3), 1.83 (3H, s, 17-CH3),
2.10 (3H, s, 18-CH3), 1.07 (3H, s, 19-CH3), 5.57 (1H,
s, H-20a), 5.10 (1H, s, H-20b), 2.06 (3H, s, 2-
OCOCH3), 2.04 (3H, s, 7-OCOCH3), 2.13 (3H, s,
9-OCOCH3), 2.03 (3H, s, 10-OCOCH3), 6.23 (1H, d,
J = 15.9 Hz, H-2′), 7.69 (1H, d, J = 15.9 Hz, H-3′),
7.64 (2H, m, H-5′, 9′), 7.44 (3H, m, H-6′～8′)；
13C-NMR (125 MHz, CDCl3) δ: 51.3 (C-1), 68.2
(C-2), 41.8 (C-3), 138.6 (C-4), 76.2 (C-5), 34.6 (C-6),
68.8 (C-7), 46.8 (C-8), 75.3 (C-9), 71.2 (C-10), 64.3
(C-11), 59.2 (C-12), 208.2 (C-13), 38.1 (C-14), 38.3
(C-15), 28.9 (C-16), 25.4 (C-17), 15.3 (C-18), 13.5
(C-19), 120.6 (C-20), 165.7 (C-1′), 116.4 (C-2′), 147.0
(C-3′), 134.0 (C-4′), 128.5 (C-5′, 9′), 129.2 (C-6′, 8′),
130.6 (C-7′), 21.2～ 20.5 (4×OCOCH3), 169.2～
170.4 (4×OCOCH3)。以上数据与文献报道一致[8]，
故鉴定化合物5为2α, 7β, 9α, 10β-四乙酰基-5α-桂皮
酰基-11, 12-环氧紫杉烷- 4(20)-烯-13-酮。
化合物 6：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 1.78 (1H, m, H-1), 1.90 (1H, m,
H-2a), 1.78 (1H, m, H-2b), 3.05 (1H, d, J = 5.6 Hz,
H-3), 5.52 (1H, dd, J =2.3, 3.7 Hz, H-5), 2.05 (1H, m,
H-6a), 1.78 (1H, m, H-6b), 5.63 (1H, dd, J = 11.7, 5.0
Hz, H-7), 5.86 (1H, d, J = 11.0 Hz, H-9), 6.26 (1H, d,
J = 11.0 Hz, H-10), 4.53 (1H, brdd, J = 9.7, 5.2 Hz,
H-13), 2.81 (1H, dd, J = 15.5, 5.2 Hz, H-14a), 1.10
(1H, dd, J = 15.5, 5.2 Hz, H-14b), 0.96 (3H, s,
16-CH3), 1.56 (3H, s, 17-CH3), 2.39 (3H, s, 18-CH3),
0.85 (3H, s, 19-CH3), 5.34 (1H, s, H-20a), 5.00 (1H, s,
H-20b), 2.05 (3H, s, 7-OAc), 2.02 (3H, s, 9-OAc),
1.98 (3H, s, 10-OAc), 6.68 (1H, d, J = 15.9 Hz, H-2′),
7.70 (1H, d, J = 15.9 Hz, H-3′), 7.53 (2H, m, H-5′, 9′),
7.37 (3H, m, H-6′～8′)；13C-NMR (125 MHz, CDCl3)
δ: 40.1 (C-1), 27.2 (C-2), 37.7 (C-3), 146.5 (C-4), 75.0
(C-5), 34.0 (C-6), 69.9 (C-7), 46.3 (C-8), 76.7 (C-9),
72.3 (C-10), 134.3 (C-11), 141.8 (C-12), 67.9 (C-13),
36.4 (C-14), 38.8 (C-15), 31.8 (C-16), 26.5 (C-17),
16.0 (C-18), 13.0 (C-19), 115.7 (C-20), 166.2 (C-1′),
117.6 (C-2′), 146.6 (C-3′), 134.3 (C-4′), 128.2 (C-5′,
9′), 129.0 (C-6′, 8′), 130.4 (C-7′), 21.2, 20.7, 20.9
(3×OCOCH3), 169.2, 169.6, 170.1 (3×OCOCH3)。以
上数据与文献报道一致[9]，故鉴定化合物6为7β, 9α,
10β-三乙酰基-5α-桂皮酰基紫杉烷-4(20), 11-烯-
13α-醇。
化合物 7：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 2.09 (1H, dd, J = 7.1, 1.9 Hz,
H-1), 5.47 (1H, dd, J = 5.9, 1.9 Hz, H-2), 3.56 (1H, d,
J = 5.9 Hz, H-3), 4.17 (1H, t, J = 2.5 Hz, H-5), 1.76
(1H, m, H-6a), 1.62 (1H, m, H-6b), 1.70 (1H, m, H-7),
4.28 (1H, d, J = 9.6 Hz, H-9), 5.88 (1H, d, J = 9.6 Hz,
H-10), 2.75 (1H, dd, J = 19.6, 7.1 Hz, H-14a), 2.34
(1H, d, J = 7.1 Hz, H-14b), 1.11 (3H, s, 16-CH3), 1.63
(3H, s, 17-CH3), 2.21 (3H, s, 18-CH3), 1.06 (3H, s,
19-CH3), 5.11 (1H, s, H-20a), 4.80 (1H, t, J = 1.4 Hz,
H-20b), 2.13 (3H, s, 2-OCOCH3), 2.06 (3H, s,
10-OCOCH3)；13C-NMR (125 MHz, CDCl3) δ: 48.7
(C-1), 70.1 (C-2), 40.9 (C-3), 147.5 (C-4), 76.4 (C-5),
30.6 (C-6), 25.2 (C-7), 45.0 (C-8), 75.8 (C-9), 76.6
(C-10), 150.2 (C-11), 138.3 (C-12), 199.7 (C-13), 36.1
(C-14), 37.9 (C-15), 37.0 (C-16), 25.6 (C-17), 14.0
(C-18), 17.5 (C-19), 113.6 (C-20), 21.2 (2-OCOCH3),
21.4 (10-OCOCH3), 170.2 (2-OCOCH3), 169.6 (10-
OCOCH3)。以上数据与文献报道一致[6]，故鉴定化
合物 7 为 9-去乙酰基紫杉宁 A。
化合物 8：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 2.36 (1H, brd, J = 11.0 Hz,
H-1), 5.49 (1H, dd, J = 9.5, 2.0 Hz, H-2), 3.52 (1H, d,
J = 9.5 Hz, H-3), 4.34 (1H, t, J = 2.8 Hz, H-5), 2.14
(1H, m, H-6α), 1.60 (1H, m, H-6β), 5.36 (1H, dd, J =
10.5, 5.0 Hz, H-7), 4.91 (1H, d, J = 3.5 Hz, H-9), 5.35
(1H, d, J = 3.5 Hz, H-10), 2.64 (1H, d, J = 18.5 Hz,
H-14α), 3.02 (1H, dd, J = 18.5, 11.5 Hz, H-14β), 4.15
(1H, d, J = 8.0 Hz, H-16α), 3.67 (1H, d, J = 8.0 Hz,
H-16β), 5.25 (1H, brs, H-20a), 4.45 (1H, brs, H-20b),
4.07 (1H, s, 11-OH), 2.08 (3H, s, 2-OAc), 2.07 (3H, s,
7-OAc), 2.01 (3H, s, 9-OAc), 1.94 (3H, s, 10-OAc),
1.50 (3H, s, H-17), 1.14 (3H, s, H-18), 1.03 (3H, s,
H-19)；13C-NMR (125 MHz, CDCl3) δ: 49.3 (C-1),
68.7 (C-2), 38.2 (C-3), 144.3 (C-4), 73.2 (C-5), 39.4
(C-6), 68.2 (C-7), 46.7 (C-8), 75.9 (C-9), 63.9 (C-10),
中草药 Chinese Traditional and Herbal Drugs 第 44 卷 第 11 期 2013 年 6 月

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80.3 (C-11), 91.8 (C-12), 205.4 (C-13), 34.9 (C-14),
49.7 (C-15), 82.0 (C-16), 15.6 (C-17), 11.8 (C-18),
13.5 (C-19), 113.1 (C-20), 20.5 (2, 7-OCOCH3), 21.2
(9-OCOCH3), 21.3 (10-OCOCH3), 168.4 (10-
OCOCH3), 172.3 (2-OCOCH3), 169.8 (9-OCOCH3),
168.4 (10-OCOCH3)。以上数据与文献对照一致[10]，
故鉴定化合物 8 为 5α-去桂皮酰基紫杉欧吉酚。
化合物 9：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 5.33 (1H, d, J = 3.3 Hz, H-2),
3.07 (1H, d, J = 3.3 Hz, H-3), 4.20 (1H, t, J = 2.8 Hz,
H-5), 2.04 (1H, m, H-6a), 1.89 (1H, m, H-6b), 4.26
(1H, dd, J = 11.4, 4.3 Hz, H-7), 4.60 (1H, d, J = 10.6
Hz, H-9), 6.02 (1H, d, J = 10.6 Hz, H-10), 6.05 (1H,
m, H-13), 2.50 (1H, dd, J = 15.2, 10.0 Hz, H-14a),
1.87 (1H, m, H-14b), 1.23 (3H, s, 16-CH3), 1.52 (3H,
s, 17-CH3), 2.15 (3H, s, 18-CH3), 1.39 (3H, s,
19-CH3), 3.47 (1H, d, J = 5.3 Hz, H-20a), 2.32 (1H, d,
J = 5.3 Hz, H-20b), 2.18 (3H, s, 13-OCOCH3), 2.13
(3H, s, 2-OCOCH3), 2.09 (3H, s, 9-OCOCH3), 2.04
(3H, s, 10-OCOCH3)；13C-NMR (125 MHz, CDCl3) δ:
75.9 (C-1), 72.5 (C-2), 40.1 (C-3), 58.3 (C-4), 78.0
(C-5), 32.9 (C-6), 69.5 (C-7), 46.5 (C-8), 78.3 (C-9),
74.0 (C-10), 136.1 (C-11), 140.3 (C-12), 71.0 (C-13),
38.4 (C-14), 43.3 (C-15), 28.3 (C-16), 21.9 (C-17),
15.3 (C-18), 13.4 (C-19), 49.8 (C-20), 20.8 (10-
OCOCH3), 21.1 (2-OCOCH3), 21.2 (9-OCOCH3),
21.6 (13-OCOCH3), 168.8～ 171.2 (2, 9, 10, 13-
OCOCH3)。以上数据与文献报道一致[11]，故鉴定化
合物 9 为 2α, 5α, 10β, 13α-四乙酰基-1β, 7β, 9α-三羟
基-4, 20-环氧紫杉烷-11-烯。
化合物 10：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 1.94 (1H, m, H-1), 4.19 (1H,
brd, J = 5.3 Hz, H-2), 3.15 (1H, d, J = 5.3 Hz, H-3),
4.31 (1H, m, H-5), 1.98 (1H, m, H-6a), 1.64 (1H, m,
H-6b), 5.50 (1H, m, H-7), 5.71 (1H, d, J = 10.8 Hz,
H-9), 6.10 (1H, d, J = 10.8 Hz, H-10), 4.34 (1H, m,
H-13), 2.72 (1H, dd, J = 16.0, 9.3 Hz, H-14a), 1.33
(1H, dd, J = 16.0, 4.6 Hz, H-14b), 0.93 (3H, s, H-16),
1.57 (3H, s, H-17), 2.26 (3H, s, H-18), 0.97 (3H, s,
H-19), 5.47 (1H, brs, H-20a), 5.30 (1H, brs, H-20b),
2.04 (3H, s, OCOCH3), 2.01 (3H, s, OCOCH3), 1.96
(3H, s, OCOCH3)；13C-NMR (125 MHz, CDCl3) δ:
50.8 (C-1), 68.6 (C-2), 42.3 (C-3), 144.0 (C-4), 75.0
(C-5), 38.3 (C-6), 70.1 (C-7), 47.7 (C-8), 75.8 (C-9),
72.2 (C-10), 132.8 (C-11), 142.2 (C-12), 68.0 (C-13),
32.0 (C-14), 36.9 (C-15), 32.4 (C-16), 26.0 (C-17),
16.9 (C-18), 13.0 (C-19), 117.5 (C-20), 20.6, 21.9,
21.3 (OCOCH3×3), 167.2, 169.7, 168.5 (7, 9, 10-
OCOCH3)。以上数据与文献对照一致[12]，故鉴定化
合物 10 为 7β, 9α, 10β-三乙酰基-2α, 5α, 13α-三羟基
紫杉烷-4(20), 11-二烯。
化合物 11：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 6.06 (1H, d, J = 7.4 Hz, H-2),
3.01 (1H, d, J = 7.4 Hz, H-3), 4.88 (1H, d, J = 8.5 Hz,
H-5), 2.57 (1H, m, H-6a), 1.84 (1H, m, H-6b), 4.21
(1H, t, J = 8.4 Hz, H-7), 4.69 (1H, s, OH-7), 4.32 (1H,
dd, J = 9.9, 3.6 Hz, H-9), 4.75 (1H, d, J = 3.6 Hz,
9-OH), 4.55 (1H, dd, J = 9.9, 4.4 Hz, H-10), 4.11 (1H,
d, J = 4.4 Hz, 10-OH), 4.58 (1H, m, H-13), 2.25 (1H,
dd, J = 14.7, 7.4 Hz, H-14a), 1.76 (1H, dd, J = 14.7,
6.7 Hz, H-14b), 3.63 (1H, s, 15-OH), 1.05 (3H, s,
H-16), 1.10 (3H, s, H-17), 1.94 (3H, s, H-18), 1.86
(3H, s, H-19), 4.44 (1H, d, J = 7.8 Hz, H-20a), 4.08
(1H, d, J = 7.8 Hz, H-20b), 2.20 (3H, s, OCOCH3),
8.00 (2H, d, J = 7.3 Hz, Bz-H-2′, 6′), 7.45 (2H, t, J =
8.1 Hz, Bz-H-3′, 5′), 7.59 (1H, t, J = 7.2 Hz, Bz-H-4′)；
13C-NMR (125 MHz, CDCl3) δ: 67.6 (C-1), 68.6
(C-2), 44.5 (C-3), 80.4 (C-4), 84.9 (C-5), 37.2 (C-6),
72.3 (C-7), 42.6 (C-8), 80.6 (C-9), 68.6 (C-10), 137.3
(C-11), 146.8 (C-12), 77.6 (C-13), 39.7 (C-14), 76.5
(C-15), 27.7 (C-16), 24.9 (C-17), 11.3 (C-18), 12.2
(C-19), 74.7 (C-20), 22.4 (4-OCOCH3), 171.0 (4-
OCOCH3), 166.1 (Ar-CO), 129.9 (C-1′), 129.6 (C-2′,
6′), 128.6 (C-3′, 5′), 133.5 (C-4′)。以上数据与文献报
道一致[13]，故鉴定化合物 11 为 7, 9, 10, 13-tetra-O-
deacetylabeobaccatin VI。
化合物 12：白色粉末状固体（丙酮）。1H-NMR
(500 MHz, CDCl3) δ: 5.88 (1H, brs, H-2), 3.07 (1H, d,
J = 7.6 Hz, H-3), 4.90 (1H, d, J = 8.1 Hz, H-5), 2.49
(1H, m, H-6a), 1.84 (1H, m, H-6b), 5.36 (1H, t, J = 7.3
Hz, H-7), 5.72 (1H, brd, J = 10.0 Hz, H-9), 4.55 (1H,
d, J = 10.0 Hz, H-10), 3.50 (1H, brs, 10-OH), 4.48
(1H, m, H-13), 1.70 (1H, brs, 13-OH), 2.12 (1H, m,
H-14a), 1.48 (1H, dd, J = 14.9, 7.2 Hz, H-14b), 1.03
(3H, s, H-16), 1.20 (3H, s, H-17), 1.92 (3H, s, H-18),
1.63 (3H, s, H-19), 4.48 (1H, d, J = 6.9 Hz, H-20a),
中草药 Chinese Traditional and Herbal Drugs 第 44 卷 第 11 期 2013 年 6 月

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4.38 (1H, d, J = 6.9 Hz, H-20b), 2.00～2.14 (各 3H, s,
2, 4, 7, 9-OCOCH3)；13C-NMR (125 MHz, CDCl3) δ:
66.7 (C-1), 68.1 (C-2), 43.8 (C-3), 79.8 (C-4), 84.9
(C-5), 34.7 (C-6), 70.1 (C-7), 43.3 (C-8), 79.2 (C-9),
66.5 (C-10), 138.6 (C-11), 145.4 (C-12), 77.5 (C-13),
39.5 (C-14), 76.7 (C-15), 27.6 (C-16), 25.9 (C-17),
11.0 (C-18), 12.9 (C-19), 74.8 (C-20), 21.2～22.2 (2,
4, 7, 9-OCOCH3)。以上数据与文献报道一致[14]，故
鉴定化合物 12 为 taxacustin。
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