中草药  2015, Vol. 46 Issue (3): 320-324
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引用本文doi: 10.7501/j.issn.0253-2670.2015.03.002
曾仁韬, 何毅仁, 沈云亨. 贡山三尖杉枝叶中倍半萜类化学成分研究[J]. 中草药, 2015, 46(3): 320-324.
ZENG Ren-tao, HE Yi-ren, SHEN Yun-heng. Sesquiterpenoids from branches and leaves of Cephalotaxus lanceolata[J]. Chinese Traditional and Herbal Drugs, 2015, 46(3): 320-324.
贡山三尖杉枝叶中倍半萜类化学成分研究
曾仁韬, 何毅仁, 沈云亨     
第二军医大学药学院, 上海 200433
收稿日期: 2014-12-18;
作者简介：曾仁韬,硕士在读,研究方向为天然药物化学.E-mail:rentaozeng09@sina.com
通讯作者：沈云亨,男,博士,副教授,硕士生导师,主要从事结构新颖天然产物小分子的发现及功能研究,生物活性小分子结构修饰及构效关系研究.E-mail:shenyunheng@hotmail.com
摘要：目的 研究贡山三尖杉Cephalotaxus lanceolata枝叶的化学成分.方法 运用硅柱色谱、凝胶柱色谱、中压制备液相、高压制备液相等方法进行分离纯化,通过波谱技术和和化学方法鉴定化合物的结构.结果 从贡山三尖杉枝叶95%乙醇提取物中分离得到11个倍半萜类化合物,分别鉴定为贡山三尖杉倍半萜A(1)、贡山三尖杉倍半萜B(2)、贡山三尖杉倍半萜C(3)、9-hydroxy-4,7-megastigmadien-3-one(4)、corchoionol C(5)、9,10-dihydroxy-4,7-megastigmadien-3-one(6)、5,12-epoxy-9-hydroxy-7-megastigmen-3-one(7)、5,12-epoxy-6,9-hydroxy-7-megastigmen-3-one(8)、loliolide(9)、(3S,5R,8S)- 5,8-epoxy-6-megastigmadien-3,9-diol(10)、clovandiol(11).结论 化合物1为未见文献报道的新化合物,2、3为2个尚未命名的新的天然产物,4～11均为首次从该种植物中分离得到.
关键词： 贡山三尖杉     倍半萜     贡山三尖杉倍半萜A     贡山三尖杉倍半萜B     贡山三尖杉倍半萜C     loliolide     clovandiol    
Sesquiterpenoids from branches and leaves of Cephalotaxus lanceolata
ZENG Ren-tao, HE Yi-ren, SHEN Yun-heng    
School of Pharmacy, Second Military Medical University, Shanghai 200433, China
Abstract: Objective To isolate and identify the chemical constituents from the branches and leaves of Cephalotaxus lanceolata. Methods The compounds were separated and purified by column chromatography with silica gel, Sephadex LH-20, MPLC, and HPLC. Their structures were elucidated on the basis of spectroscopic methods. Results Eleven sesquiterpenoids were isolated from 95% ethanol extract of the branches and leaves of C. lanceolata and identified as lanceoloside A (1), lanceoloside B (2), lanceoloside C (3), 9-hydroxy-4,7-megastigmadien-3-one (4), corchoionol C (5), 9,10-dihydroxy-4,7-megastigmadien-3-one (6), 5,12-epoxy-9- hydroxy-7-megastigmen-3-one (7), 5,12-epoxy-6,9-hydroxy-7-megastigmen-3-one (8), loliolide (9), (3S,5R,8S)-5,8-epoxy-6- megastigmadien-3,9-diol (10), and clovandiol (11) respectively. Conclusion Compounds 1 is identified as a new sesquiterpenoid, while compounds 2—3 are two new natural products. Compounds 4—11 are isolated from this plant for the first time.
Key words: Cephalotaxus lanceolata K. M. Feng     sesquiterpenoids     lanceoloside A     lanceoloside B     lanceoloside C     loliolide     clovandiol    

贡山三尖杉Cephalotaxus lanceolata K. M. Feng是三尖杉科（Cephalotaxaceae）三尖杉属Cephalotaxus Sieb. et Zucc.ex Endl. 植物，其果实入药有润肺、止咳、消积之效[1]。国内外对该属植物的研究主要集中在生物碱[2, 3, 4, 5, 6, 7, 8]、黄酮[9]、二萜[10, 11, 12]等成分，而对其倍半萜类成分报道很少；对贡山三尖杉的研究也很少[13]。为了寻找更多结构新颖的活性成分，本课题组对产自云南省贡山县高黎贡山的贡山三尖杉枝叶95%乙醇提取物进行系统化学成分研究，从中分离得到11个倍半萜类化合物（图 1），分别鉴定为贡山三尖杉倍半萜A（lanceoloside A，1）、贡山三尖杉倍半萜B（lanceoloside B，2）、贡山三尖杉倍半萜C（lanceoloside C，3）、9-hydroxy-4,7-megastigmadien- 3-one（4）、corchoionol C（5）、9,10-dihydroxy-4,7- megastigmadien-3-one（6）、5,12-epoxy-9-hydroxy-7- megastigmen-3-one（7）、5,12-epoxy-6,9-hydroxy-7- megastigmen-3-one（8）、loliolide（9）、(3S,5R,8S)-5,8- epoxy-6-megastigmadien-3,9-diol（10）、clovandiol（11）。化合物1为未见文献报道的新化合物，化合物2～3为2个新天然产物，化合物4～11均为首次从该种植物中分离得到。

图 1 化合物1～11的结构Fig.1 Structures of compounds 1—11
1 仪器与材料

薄层色谱硅胶GF254（烟台江友硅胶开发有限公司）、柱色谱硅胶（200～300目）；Sephadex LH-20（40～70 μm）填料（美国GE公司），ODS填料（日本YMC公司）；薄层色谱制备板（烟台江友硅胶开发有限公司）；AVANCE-400、500 MHz核磁共振波谱仪（瑞士Bruker公司）；Agilent LC/MSD和Agilent Q-TOF高分辨质谱仪（美国Agilent公司）；Bruker FTIR Vector 22红外光谱仪（瑞士Bruker公司）；Shimadzu UV-2550分光光度计（日本Shimadzu公司）；Perkin-Elmer 341数字旋光仪（美国Perkin- Elmer公司）；Buchi Sepacore C-615中压制备色谱系统（瑞士Buchi公司）。

贡山三尖杉全草于2010年8月采自云南省怒江州贡山县高黎贡山，经云南省怒江州民族医药研究所周元川所长鉴定为贡山三尖杉Cephalotaxus lanceolata K. M. Feng，植物标本（201008070）现保存在第二军医大学药学院天然药化教研室标本室。

2 提取与分离

贡山三尖杉干燥枝叶9.3 kg，粉碎，用95%乙醇冷浸提取3次，每次48 h，提取液浓缩后以2%～3% HCl调节pH至2～3，滤过，滤液用CHCl3萃取除去非生物碱成分后水层用饱和Na2CO3调节pH至10，CHCl3萃取得到总生物碱9 g，不溶于HCl的滤渣和CHCl3萃取过的水层分别用石油醚、醋酸乙酯萃取，减压回收得醋酸乙酯部位135 g；将醋酸乙酯部位经常压硅胶柱色谱分离，石油醚-醋酸乙酯（100∶1、50∶1、30∶1、10∶1、5∶1、1∶1）梯度洗脱，得到8个流分Fr. 1～8。将Fr. 3（7.2 g）依次经过Sephadex LH-20（甲醇）及硅胶柱色谱分离，得到化合物1（15 mg）、4（6 mg）、6（21 mg）9（3 mg）；Fr. 5（12.8 g）经过反相中压制备色谱，甲醇-水（40%～100%）梯度洗脱，得到6个部分Fr. 5-1～5-6。将Fr. 5-2（140 mg）经过Sephadex LH-20（甲醇）及硅胶柱色谱分离纯化，得到化合物2（7 mg）、3（9 mg）、7（15 mg）和8（7 mg）；将Fr. 5-5（270 mg）依次经过Sephadex LH-20（甲醇）及硅胶柱色谱分离纯化，得到化合物5（30 mg）、10（5 mg）、11（13 mg）。

3 结构鉴定

化合物1：白色无定形粉末，[α]D20 +117.8°（c 0.09, MeOH）；IRv manKBr(cm−1): 3 376, 2 931, 1 639, 1 076, 1 037。高分辨质谱HR-ESI-MS给出准分子离子峰 [M＋H]+ m/z: 225.141 2（计算值225.141 7），结合1H-NMR和13C-NMR，确定分子式为C13H20O3，不饱和度为4。根据1H-NMR、13C-NMR和DEPT谱（表 1）中的信息，可以判断该化合物含有3个季碳，其中2个sp2季碳 (δC 201.8 s, 165.9 s) 和1个sp3季碳 (δC 42.3 s)；5个次甲基，其中1个连氧的次甲基 (δH 4.29 m, δC 68.9 d)；2个亚甲基，其中有1个连氧的亚甲基 [δH 3.37 (d, J = 10.9 Hz)；3.34 (d, J = 10.9 Hz), δC 68.8 t]；3个甲基 [δH 1.93 (d, J = 0.8 Hz), δC 23.9 q]；[δH 1.25 (d, J = 6.4 Hz), δC 23.8 q]；(δH 0.96 s, δC 21.9 q)。通过HMBC谱（图 2），比较3个甲基的相关信号，可以推测出连氧的亚甲基可能在C-11或C-12位。由此化合物1的平面结构基本确定。再分析化合物的CD [θ]25 (c 0.5, MeOH)：+57 000 (246)，−3 600 (319)，与已知化合物9-hydroxy- 4,7-megastigmadien-3-one基本一致[14]，可以判断6位H的构型为α。在NOESY谱（图 2）中，H-6与连氧亚甲基的2个H分别相关，由此可以确定-OH与C-11相连。综上所述，确定化合物1的结构（图 1），命名为贡山三尖杉倍半萜A（lanceoloside A）。

表 1 化合物1的1H-NMR (400 MHz, CD3OD)、13C-NMR (100 MHz, CD3OD) 和DEPT谱数据 Table 1 1H-NMR (400 MHz, CD3OD), 13C-NMR (100 MHz, CD3OD), and DEPT spectroscopic data of compound 1

图 2 化合物1关键的HMBC 和 NOESY相关信号Fig.2 Key HMBC and NOESY correlations of compound 1

化合物2：无色油状物。ESI-MS m/z: 251 [M＋Na]+, 227 [M－H]−，推测其相对分子质量为228。结合1H-NMR和13C-NMR推测其分子式为C13H24O3，不饱和度为2。1H-NMR (400 MHz, CD3OD) δ: 1.82 (1H, dd, J = 13.2, 7.1 Hz, H-2a), 1.64 (1H, brt, J = 13.0 Hz, H-2b), 4.17 (1H, m, H-3), 1.98 (1H, dd, J = 13.1, 7.0 Hz, H-4a), 1.56 (1H, dd, J = 13.1, 10.0 Hz, H-4b), 1.35 (1H, m, H-6), 1.49 (1H, m, H-7a), 1.84 (1H, m, H-7b), 1.70 (1H, m, H-8a), 1.78 (1H, m, H-8b), 4.28 (1H, m, H-9), 1.25 (3H, d, J = 6.5 Hz, H-10), 0.94 (3H, s, H-11), 3.46 (1H, dd, J = 8.0, 2.0 Hz, H-12a), 3.76 (1H, d, J = 8.1 Hz, H-12b), 1.16 (3H, s, H-13)；13C-NMR (100 MHz, CD3OD) δ: 45.9 (C-1), 49.8 (C-2), 67.1 (C-3), 50.5 (C-4), 86.1 (C-5), 56.8 (C-6), 22.5 (C-7), 40.5 (C-8), 69.1 (C-9), 23.6 (C-10), 20.4 (C-11), 77.3 (C-12), 23.8 (C-13)。以上数据与文献报道基本一致[15]，故鉴定化合物2为1个新的天然产物，之前并未命名，故将其命名为贡山三尖杉倍半萜B（lanceoloside B）。

化合物3：无色油状物。ESI-MS m/z: 249 [M＋Na]+，推测其相对分子质量为226。结合1H-NMR和13C-NMR推测其分子式为C13H22O3，不饱和度为3。1H-NMR (400 MHz, CD3OD) δ: 1.81 (1H, dd, J = 13.1, 7.0 Hz, H-2a), 1.64 (1H, brt, J = 13.1 Hz, H-2b), 4.17 (1H, m, H-3), 1.97 (1H, dd, J = 13.0, 7.0 Hz, H-4a), 1.55 (1H, dd, J = 13.0, 10.0 Hz, H-4b), 2.04 (1H, d, J = 9.0 Hz, H-6), 5.51 (1H, ddd, J = 15.4, 10.3, 1.1 Hz, H-7), 5.61 (1H, dd, J = 15.4, 5.9 Hz, H-8), 4.28 (1H, m, H-9), 1.24 (3H, d, J = 6.5 Hz, H-10), 0.95 (3H, s, H-11), 3.46 (1H, dd, J = 8.0, 2.0 Hz, H-12a), 3.76 (1H, d, J = 8.0 Hz, H-12b), 1.11 (3H, s, H-13)；13C-NMR (100 MHz, CD3OD) δ: 45.5 (C-1), 48.7 (C-2), 67.1 (C-3), 49.3 (C-4), 85.6 (C-5), 61.9 (C-6), 127.5 (C-7), 139.6 (C-8), 69.2 (C-9), 23.9 (C-10), 20.6 (C-11), 77.6 (C-12), 24.1 (C-13)。以上数据与文献报道基本一致[16]，故鉴定化合物3为1个新的天然产物，之前未命名，故将其命名为贡山三尖杉倍半萜C（lanceoloside C）。

化合物4：无色油状物。ESI-MS m/z: 231 [M＋Na]+, 207 [M－H]−，推测其相对分子质量为208。结合1H-NMR和13C-NMR推测其分子式为C13H20O2，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 2.06 (1H, d, J = 16.8 Hz, H-2a), 2.32 (1H, d, J = 16.8 Hz, H-2b), 5.89 (1H, s, H-4), 2.54 (1H, d, J = 8.2 Hz, H-6), 5.54 (1H, dd, J = 15.5, 8.2 Hz, H-7), 5.56 (1H, dd, J = 15.5, 5.6 Hz, H-8), 4.34 (1H, m, H-9), 1.28 (3H, d, J = 6.6 Hz, H-10), 1.03 (3H, s, H-11), 0.97 (3H, s, H-12), 1.88 (3H, d, J = 1.2 Hz, H-13)；13C-NMR (100 MHz, CD3OD) δ: 37.3 (C-1), 48.5 (C-2), 202.1 (C-3), 126.3 (C-4), 166.2 (C-5), 56.8 (C-6), 127.3 (C-7), 140.4 (C-8), 68.9 (C-9), 23.9 (C-10), 27.4 (C-11), 28.2 (C-12), 23.8 (C-13)。以上数据与文献报道基本一致[14]，故鉴定化合物4为9-hydroxy-4,7-megastigmadien-3-one。

化合物5：无色油状物。ESI-MS m/z: 247 [M＋Na]+, 223 [M－H]−，推测相对分子质量为224。结合1H-NMR和13C-NMR推测其分子式为C13H20O3，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 2.14 (1H, d, J = 17.2 Hz, H-2a), 2.5 (1H, d, J = 17.0 Hz, H-2b), 5.86 (1H, s, H-4), 5.78 (1H, overlap, H-7), 5.78 (1H, overlap, H-8), 4.31 (1H, m, H-9), 1.22 (3H, d, J = 6.5 Hz, H-10), 1.02 (3H, s, H-11), 0.99 (3H, s, H-12), 1.91 (3H, d, J = 1.4 Hz, H-13)；13C-NMR (100 MHz, CD3OD) δ: 42.6 (C-1), 50.8 (C-2), 201.3, (C-3), 127.1 (C-4), 167.6 (C-5), 80.0 (C-6), 130.1 (C-7), 137.0 (C-8), 68.8 (C-9), 24.0 (C-10), 23.9 (C-11), 24.6 (C-12), 19.7 (C-13)。以上数据与文献报道基本一致[17]，故鉴定化合物5为corchoionol C。

化合物6：无色油状物。ESI-MS m/z: 247 [M＋Na]+, 223 [M－H]−，推测相对分子质量为224。结合1H-NMR和13C-NMR推测其分子式为C13H20O3，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 2.09 (1H, d, J = 16.4 Hz, H-2a), 2.33 (1H, d, J = 16.8 Hz, H-2b), 5.91 (1H, s, H-4), 2.55 (1H, d, J = 9.0 Hz, H-6), 5.71 (1H, dd, J = 15.2, 9.0 Hz, H-7), 5.62 (1H, dd, J = 15.2, 5.5 Hz, H-8), 4.30 (1H, m, H-9), 3.69 (1H, dd, J = 11.0, 3.5 Hz, H-10a), 3.50 (1H, dd, J = 11.0, 7.4 Hz, H-10b), 1.03 (3H, s, H-11), 0.96 (3H, s, H-12), 1.90 (3H, d, J = 1.6 Hz, H-13)；13C-NMR (100 MHz, CD3OD) δ: 42.3 (C-1), 44.6 (C-2), 201.8 (C-3), 126.8 (C-4), 165.9 (C-5), 50.8 (C-6), 126.5 (C-7), 140.8 (C-8), 68.9 (C-9), 68.8 (C-10), 23.8 (C-11), 23.9 (C-12), 21.9 (C-13)。以上数据与文献报道基本一致[18]，故鉴定化合物6为9,10-dihydroxy-4,7-megastigmadien-3-one。

化合物7：无色油状物。ESI-MS m/z: 247 [M＋Na]+, 471 [2M＋Na]+，推测相对分子质量为224。结合1H-NMR和13C-NMR推测其分子式为C13H20O3，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 1.94 (1H, d, J = 16.6 Hz, H-2a), 2.31 (1H, d, J = 16.6 Hz, H-2b), 2.21 (1H, dt, J = 17.1, 1.6 Hz, H-4a), 2.57 (1H, d, J = 17.1 Hz, H-4b), 2.41 (1H, d, J = 9.1 Hz, H-6), 5.74 (1H, overlap, H-7), 5.74 (1H, overlap, H-8), 4.30 (1H, m, H-9), 1.22 (3H, d, J = 6.2 Hz, H-10), 1.03 (3H, s, H-11), 3.61 (1H, dd, J = 8.0, 2.8 Hz, H-12a), 3.68 (1H, d, J = 8.0 Hz, H-12b), 1.16 (3H, s, H-13)；13C-NMR (100 MHz, CD3OD) δ: 45.4 (C-1), 49.9 (C-2), 211.8 (C-3), 51.1 (C-4), 85.0 (C-5), 59.6 (C-6), 123.4 (C-7), 143.3 (C-8), 69.0 (C-9), 24.1 (C-10), 20.5 (C-11), 80.0 (C-12), 24.5 (C-13)。以上数据与文献报道基本一致[19]，故鉴定化合物7为5,12-epoxy-9- hydroxy-7-megastigmen-3- one。

化合物8：无色油状物。ESI-MS m/z: 263 [M＋Na]+, 239 [M－H]−，推测相对分子质量为240。结合1H-NMR和13C-NMR推测其分子式为C13H24O4，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 1.91 (1H, d, J = 16.6 Hz, H-2a), 2.35 (1H, d, J = 16.6 Hz, H-2b), 2.21 (1H, dt, J = 17.1, 1.6 Hz, H-4a), 2.57 (1H, d, J = 17.1 Hz, H-4b), 6.08 (1H, d, J = 16.3 Hz, H-7), 6.04 (1H, dd, J = 16.3, 5.1 Hz, H-8), 4.37 (1H, m, H-9), 1.22 (3H, d, J = 6.5 Hz, H-10), 0.96 (3H, s, H-11), 3.67 (1H, dd, J = 8.0, 2.8 Hz, H-12a), 3.75 (1H, d, J = 8.0 Hz, H-12b), 1.12 (3H, s, H-13)；13C-NMR (100 MHz, CD3OD) δ: 48.6 (C-1), 52.9 (C-2), 208.7 (C-3), 53.7 (C-4), 82.1 (C-5), 86.5 (C-6), 125.1 (C-7), 140.7 (C-8), 68.2 (C-9), 24.3 (C-10), 15.7 (C-11), 77.9 (C-12), 19.4 (C-13)。以上数据与文献报道基本一致[20]，故鉴定化合物8为5,12-epoxy-6,9-hydroxy-7- megastigmen-3-one。

化合物9：无色油状物。ESI-MS m/z: 219 [M＋Na]+, 415 [2M＋Na]+, 231 [M＋Cl]−，推测相对分子质量为196。结合1H-NMR和13C-NMR推测其分子式为C11H16O3，不饱和度为4。1H-NMR (400 MHz, CD3OD) δ: 1.55 (1H, dd, J = 3.6, 14.4 Hz, H-2a), 2.01 (1H, dd, J = 2.4, 14.4 Hz, H-2b), 4.24 (1H, m, H-3), 1.77 (1H, dd, J = 4.0, 13.6 Hz, H-4a), 2.44 (1H, dd, J = 2.8, 13.6 Hz, H-4b), 5.77 (1H, s, H-7), 1.78 (3H, s, H-9), 1.29 (3H, s, H-10), 1.48 (3H, s, H-11)；13C-NMR (100 MHz, CD3OD) δ: 37.3 (C-1), 48.0 (C-2), 67.3 (C-3), 46.5 (C-4), 89.0 (C-5), 185.7 (C-6), 113.4 (C-7), 174.5 (C-8), 27.1 (C-9), 27.5 (C-10), 31.1 (C-11)。以上数据与文献报道基本一致[21]，故鉴定化合物9为loliolide。

化合物10：无色油状物。ESI-MS m/z: 249 [M＋Na]+, 225 [M－H]−，推测相对分子质量为226。结合1H-NMR和13C-NMR推测其分子式为C13H22O3，不饱和度为3。1H-NMR (400 MHz, CD3OD) δ: 1.52 (1H, dd, J = 3.3, 13.8 Hz, H-2a), 2.05 (1H, brd, J = 14.0 Hz, H-2b), 4.49 (1H, m, H-3), 1.98 (1H, dd, J = 4.0, 13.8 Hz, H-4a), 2.62 (1H, brd, J = 14.0 Hz, H-4b), 5.76 (1H, s, H-7), 4.76 (1H, brd, J = 7.2 Hz, H-8), 3.94 (1H, m, H-9), 1.43 (3H, d, J = 6.6 Hz, H-10), 1.42 (3H, s, H-11), 1.13 (3H, s, H-12), 1.92 (3H, s, H-13)；13C-NMR (100 MHz, CD3OD) δ: 34.3 (C-1), 51.2 (C-2), 66.5 (C-3), 51.1 (C-4), 89.3 (C-5), 154.6 (C-6), 119.7 (C-7), 88.5 (C-8), 71.3 (C-9), 19.1 (C-10), 27.6 (C-11), 31.3 (C-12), 27.5 (C-13)。以上数据与文献报道基本一致[22]，故鉴定化合物10为 (3S,5R,8S)-5,8-epoxy-6-megastigmadien-3,9-diol。

化合物11：无色油状物。ESI-MS m/z: [M＋Na]+ 239，推测相对分子质量为238。结合1H-NMR和13C-NMR推测其分子式为C15H26O2，不饱和度为3。1H-NMR (400 MHz, CD3OD) δ: 3.78 (1H, dd, J = 10.6, 5.9 Hz, H-2), 1.60 (1H, m, H-3a), 1.74 (1H, m, H-3b), 1.29 (1H, m, H-5), 1.16 (1H, m, H-6a), 1.06 (1H, m, H-6b), 1.32 (1H, m, H-7a), 1.18 (1H, m, H-7b), 3.24 (1H, brs, H-9), 1.86 (1H, m, H-10a), 1.71 (1H, m, H-10b), 2.47 (1H, m, H-11a), 1.21 (1H, m, H-11b), 1.60 (2H, m, H-12), 1.03 (3H, s, H-13), 0.93 (3H, s, H-14), 1.04 (3H, s, H-15)；13C-NMR (100 MHz, CD3OD) δ: 45.6 (C-1), 81.6 (C-2), 48.3 (C-3), 36.0 (C-4), 52.2 (C-5), 27.0 (C-6), 34.6 (C-7), 37.9 (C-8), 76.1 (C-9), 28.0 (C-10), 21.9 (C-11), 36.8 (C-12), 29.3 (C-13), 31.9 (C-14), 25.9 (C-15)。以上数据与文献报道基本一致[23]，故鉴定化合物11为clovandiol。

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