扁枝石松中石杉型三萜成分研究

　　2.2.5  化合物5白色粉末，EI-MS m/z 458 ［M］+, 440, 422, 407, 391, 269, 205, 187, 1H-NMR (400 MHz, C5D5N) δ：5.44 (1H, brs, H-15), 4.44 (1H, brs, H-3), 4.10 (1H, d, J = 11.2 Hz, CH-24), 3.86 (1H, d, J = 10.8 Hz, CH′-24 ), 3.66 (1H, brs, H-21), 1.59, 1.15, 0.93, 0.89, 0.83, 0.80 (s, 6×CH3)。 13C-NMR (100 MHz, C5D5N) δ：34.2 (C-1), 26.8 (C-2), 70.0 (C-3), 44.3 (C-4), 50.3 (C-5), 19.7 (C-6), 46.0 (C-7), 38.0 (C-8), 63.1 (C-9), 38.6 (C-10), 25.5 (C-11), 27.6 (C-12), 57.4 (C-13), 139.1(C-14), 122.7 (C-15), 24.6 (C-16), 43.8 (C-17), 36.4 (C-18), 31.9 (C-19), 26.7 (C-20), 75.3 (C-21), 37.7 (C-22), 23.7 (C-23), 65.8 (C-24), 16.6 (C-25), 20.1 (C-26), 56.8 (C-27), 13.8 (C-28), 22.2 (C-29), 28.7 (C-30). 其光谱数据与文献［8］报道的14-serraten-3α, 21β, 24-triol (lycoclavanol) 基本一致。
　　
　　2.2.6  化合物6白色粉末， EI-MS m/z 488 ［M］+, 470, 452, 437, 408, 372, 250, 237, 219, 201, 187。 1H-NMR (400 MHz, C5D5N ) δ：5.45 (1H, brs, H-15), 4.69 (1H, brs, H-3), 4.37 (1H, d, J = 10.4, H-20), 3.82 (1H, brs, H-21), 1.75, 1.19, 1.12, 0.95, 0.92, 0.84 (s, 6×CH3)。 13C-NMR (100 MHz, C5D5N) δ：34.8 (C-1), 27.9 (C-2), 70.6 (C-3), 48.6 (C-4), 49.6 (C-5), 21.2 (C-6), 45.7 (C-7), 37.6 (C-8), 62.6 (C-9), 39.4 (C-10), 25.8 (C-11), 27.6 (C-12), 57.6 (C-13), 139.0 (C-14), 122.8 (C-15), 24.4 (C-16), 41.3 (C-17), 37.8 (C-18), 43.3 (C-19), 66.5 (C-20), 79.6 (C-21), 38.9 (C-22), 25.5 (C-23), 180.7 (C-24), 14.1 (C-25), 19.9 (C-26), 56.9 (C-27), 14.7 (C-28), 21.7 (C-29), 28.8 (C-30)。以上数据与文献［8］报道的3α, 20β, 21β-trihydroxy-14-serraten-24-oic acid一致。

　　2.2.7  化合物7白色粉末，ESI-MS m/z 573 ［M-H］-, 609［M+Cl］-；EI-MS m/z 488, 470, 455, 439, 277, 259, 205, 187。1H-NMR (400 MHz, C5D5N ) δ：5.46(1H, brs, 15-H), 4.78 (1H, d, J = 6.8 Hz, H-1' ), 3.38 (1H, dd, J = 11.6, 4.4 Hz, H-21), 1.28, 1.15, 0.97, 0.93, 0.80, 0.79, 0.77 (s, 7×CH3)； 13C-NMR (100 MHz, C5D5N) δ： 38.1 (C-1), 26.6 (C-2), 88.7 (C-3), 39.8 (C-4), 56.2 (C-5), 19.1 (C-6), 45.5 (C-7), 38.0 (C-8), 63.0 (C-9), 38.9 (C-10), 25.5 (C-11), 27.5 (C-12), 57.3 (C-13), 139.0 (C-14), 122.7 (C-15), 24.6 (C-16), 43.8 (C-17), 36.4 (C-18), 31.8 (C-19), 27.0 (C-20), 75.3 (C-21), 37.4 (C-22), 28.7 (C-23), 16.1 (C-24), 16.9 (C-25), 20.1 (C-26), 56.7 (C-27), 13.8 (C-28), 22.2 (C-29), 28.3 (C-30), 107.6 (C-1' ), 73.0 (C-2' ), 74.7 (C-3' ), 69.6 ( C-4' ), 66.8 (C-5' )。其光谱数据与文献［9］ 报道的21-episerratenediol-3-α-L-arabinopyranoside (inundoside E ) 一致。

　　3  讨论
   
　　石杉型三萜类化合物在氯仿、醋酸乙酯、甲醇、二甲亚砜以及水中的溶解性都比较差，仅在吡啶中能充分溶解，因此给分离纯化及体外活性筛选工作带来很大的困难。鉴于石杉型三萜具有较强的细胞毒和抗肿瘤及抗真菌活性，为了进一步揭示该类化合物的生物活性，在其结构中引入糖基，从而提高该类化合物的水溶性是非常必要的。近几年来，未见有关石杉型三萜糖苷类化合物及其生物活性的研究报道，作者从扁枝石松中分离得到一个已知的石杉型三萜糖苷类化合物，并正在对其生物活性进行试验。继续深入的研究对石杉型三萜糖苷类化合物的发现及其生物活性的阐明具有一定的科学意义。

【参考文献】
  　［1］何顺志, 徐文芬. 贵州中草药资源研究［M］.贵阳：贵州科技出版社, 2007：148.

　　［2］Ma, X Q, Gang D V. The lycopodium alkaloids［J］. Nat. Prod. Rep, 2004, 21：752.

　　［3］Tanaka R., Minami T, Ishikawa Y, et al. Cancer chemopreventive activity of serratane-typetriterpenoids on two-stage mouse mouse skin carcinogenesis［J］. Cancer Lett，2003，196：121.

　　［4］Tanaka R, Minami T, Ishikawa Y. Cancer Chemopreventive activity of Serratane-Type Triterpenoids from Picea jezoensis［J］. Chem ＆ Biodiver, 2004, 1：878.

　　［5］Zhang Zhizhen, ELSlhly H N, Jacob M R, et al. Nature products inhibiting Candida albicans secreted aspartic proteases from Lycopodium cernuum［J］. J Nat Prod, 2002, 65：979.

　　［6］Fang Jimmin, Tsai Weiyu, Cheng Yushia. Serratene triterpenes from Pinus armandii bark［J］. Phytochemistry, 1991, 30 (4)：1333.

　　［7］Zhou Hui. 蛇足石杉中性成分的研究［D］. 2002：60.

　　［8］Yan Jian, Yi Ping, Chen Baohui, et al. Polyhydroxserratane triterpenoids from Diphasiastrum complanatum［J］. Phytochemistry, 2008, 69：506.

　　［9］Tsuda Y, Kaneda M, Yasufku N, et al. The structure of inundoside A-E occurring in Lycopodium inundatum［J］. Chem. Pharm. Bull, 1981, 8：2123.