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交让木果实的化学成分研究
作者:向轶波,何红平,孔宁川,郝小江,刘祥义    
作者单位:1.西南林学院资源学院,云南 昆明 650224;2.中国科学院昆明植物研究所植物化学与西部植物可持续利用国家重点实验室,云南 昆明 650204

《时珍国医国药》 2008年 第2期

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《二十五史》在线阅读及全文检索    《四库全书·史部》在线阅读及全文检索   
       【摘要】 
       目的研究交让木果实的化学成分。方法采用硅胶,RP18,Sephadex LH20柱层析对交让木果实的乙醇提取物进行分离纯化,根据化学方法和波谱数据(ESIMS,1DNMR,2DNMR)对分离所得化合物进行结构鉴定。结果共分得了5个化合物分别为Paxdaphnine B(Ⅰ), Paxdaphnine A(Ⅱ), Daphgracine (Ⅲ),Daphgraciline (Ⅳ),Yuzurine (Ⅴ)。结论 化合物Ⅰ-Ⅴ均为虎皮楠生物碱,并且化合物Ⅰ,Ⅱ为首次从该种植物中分得。
       【关键词】  交让木果实 化学成分 虎皮楠生物碱
       Studies on the Chemical Constituents of Daphniphyllum Macropodum
       XIANG Yibo, HE Hongping,KONG Ningchuan, HAO Xiaojiang, LIU Xiangyi
       1. College of Resource, Southwest Forestry College, Yunnan Kunming 650224,China;
       2.State Key Laboratory of Phytochemistry and Plant Resources in West China, Yunnan Kunming Institute of Botany , Chinese Academy of Science, Kunming 650204,China
       Abstract:ObjectiveTo study the chemical constituents of the fruit of Daphniphyllum macropodum Miq.MethodsThe crude extract was extracted with 90% EtOH, isolated and purified on repeatedly chromatograph over silica gel, RP-18, Sephadex LH-20 column. Their chemical structures were elucidated by chemical methods and spectral data (ESIMS,1D-NMR,2D-NMR).ResultsFive compounds are isolated from the fruit of Daphniphyllum macropodum Miq., and were indentified as Paxdaphnine B(Ⅰ), Paxdaphnine A(Ⅱ), Daphgracine (Ⅲ),Daphgraciline (Ⅳ),Yuzurine (Ⅴ) respectively. ConclusionThe five compounds were Daphniphyllum alkaloids, and compoundⅠandⅡare found from Daphniphyllum macropodum Miq. for the first time.
       Key words:The fruit of Daphniphyllum macropodum Miq;  Chemical constituents;   Daphniphyllum alkaloids
       交让木Daphniphyllum macropodum Miq为虎皮楠科(Daphniphyllaceae)虎皮楠属(Daphniphyllum)植物,又名画眉珠,虎皮楠,山黄树(湖北),豆腐头(广东),枸色子、枸血子、水红朴(四川)。交让木为常绿乔木,以果实、叶和根在民间多作药用。生于海拔600~1900 m的阴湿山坡、溪谷及阔叶林中,分布于长江流域以南云南、四川、贵州、广西、广东、湖南、湖北、江西、浙江、安徽及中国台湾等省区。具有治疗疮疖肿毒,哮喘、咳嗽、风湿、炎症、感冒发热、肝脾肿大、骨折、毒蛇咬伤之功效;叶煎水喷洒,可杀灭蚜虫[1,2]。
       
       虎皮楠属植物特别代谢产生一类具有复杂的多环结构的生物碱,被称为虎皮楠生物碱(Daphniphyllum alkaloids)。从生物遗传学和全合成的角度来看,虎皮楠生物碱具有很大的研究价值[3,4]。根据最近关于交让木中虎皮楠生物碱的报道,5个结构新颖的虎皮楠生物碱被郭跃伟等从交让木的茎叶中分离得到[5,6]。本文报道了首次从交让木果实中分得5个虎皮楠生物碱,分别为Paxdaphnine B (Ⅰ), Paxdaphnine A(Ⅱ), Daphgracine (Ⅲ),Daphgraciline (Ⅳ),Yuzurine (Ⅴ)。
       1  材料与仪器
       1.1  药材 
       样品于200511采于江西庐山,由中国科学院昆明植物研究所龚洵研究员鉴定为Daphniphyllum macropodum Miq.的果实。
       1.2  仪器 
       BUCHIR-3000型旋转蒸发仪;比旋度用J-20C旋光仪器测定;红外光谱采用KBr压片以IR-450型红外光谱仪器测定;核磁共振谱用DRX500型核磁共振仪测定,TMS为内标;质谱EI-MS 用Finnigan-4510型质谱仪测定。
       1.3  试剂与材料 
       柱层析用硅胶(100~200目,200~300目,300~400目)或硅胶H(10~40μm)及薄层层析板均为青岛海洋化工厂生产。RP18,Sephadex LH-20为Pharmacia公司产品。薄层层析通过碘化铋钾显色剂显色。层析用溶剂均为分析纯。
       2  方法与结果
       2.1  提取与分离 
       交让木果实(20 kg),粉碎后经90%的乙醇回流提取3次,过滤,回收乙醇,将浓缩的提取物悬浮于4 L水中,用饱和酒石酸调pH值至3,用石油醚脱脂3次,再用氯仿萃取一次得非碱部分。将水层用氨水(NH3H2O)调pH值至9,用氯仿萃取5次,回收氯仿得总碱(47 g)。该部分经多次硅胶柱层析,Sephadex LH20凝胶层析,RP18反相柱层析后,分离得到化合物Ⅰ(22 mg),Ⅱ(6 mg),Ⅲ(7 mg),Ⅳ(8 mg),Ⅴ(15 mg)。
       2.2  结构鉴定 
       2.2.1  化合物Ⅰ
       无色针晶(丙酮)。[α]23.6  D+ 33.33 (c 0.00,  CH3OH);postive ESIMS: m/z: 346 [M + H]+;IR(KBr)νmaxcm-1:3385 (moderate), 2933, 2873, 1730, 1444, 1367, 1189, 1162, 1041, 864;HRESI m/z 346.2378 [M+H]+, calcd. for C21H32NO3 346.2382;由分子式可推测化合物Ⅰ占有7个不饱和度;1H NMR, 13C NMR和HMBC (CDCl3)数据见表1。化合物Ⅰ与文献报道Paxdaphnine B[7]波谱数据一致,故鉴定化合物Ⅰ为Paxdaphnine B,结构式为:表1  化合物Ⅰ的1H NMR(400MHz), 13C NMR(100MHz)和HMBC(500 MHz) 光谱数据(略) 
       2.2.2  化合物Ⅱ
       无色胶状物。postive ESIMS: m/z: 358 [M + H]+;从1H NMR,13C NMR,DEPT和ESIMS推测分子式为C22H31NO3;由分子式可推测化合物Ⅱ占有7个不饱和度。1H NMR(400 MHz,CDCl3)d (in ppm):3.82 (1H,d,14.4,H-1a), 3.95 (1H,d,14.4,H-1b), 2.56 (1H,m,H-3a), 2.03 (1H,m,H-3b), 1.69 (1H,m,H-4a), 1.75 (1H,m,H-4b), 2.19 (1H,m,H-6), 3.18 (1H,d,14.4,H-7a), 3.98(1H,m,H-7b), 2.11 (1H,m,H-11a), 1.92 (1H,m,H-11b), 1.49(1H,m,H-12a), 2.31(1H,m,H-12b), 1.63 (1H,m,H-13a), 2.45 (1H,m,H-13b), 3.26 (1H,m,H-14), 2.75 (1H,dd,8.8,17.5,H-15), 1.55 (1H,m,H-16a), 1.72 (1H,m,H-16b), 1.48 (1H,m,H-17a), 1.77 (1H,m,H-17b), 1.95 (1H,m,H-18a), 1.62 (1H,m,H-18b), 1.38 (3H,t,6.0,H-20), 4.03 (1H,d,8.4,H-21a), 4.23 (1H,d,8.4,H-21b), 3.68 (3H,s,OMe); 13C NMR(100 MHz,CDCl3)d (in ppm):66.0 (t,C-1), 81.8 (s,C-2), 30.4 (t,C-3), 35.9 (t,C-4), 49.3 (s,C-5), 39.6 (d,C-6), 55.1 (t,C-7), 61.4 (s,C-8), 64.9 (s,C-9), 85.3 (s,C-10), 31.4 (t,C-11), 28.2 (t,C-12), 28.5 (t,C-13), 46.8 (d,C-14), 55.1 (d,C-15), 26.7 (t,C-16), 41.8 (t,C-17), 26.9 (t,C-18), 9.9 (q,C-20), 68.4 (t,C-21), 172.6 (s,C-22), 51.7 (q, OMe)。化合物Ⅰ与文献报道Paxdaphnine A[7]波谱数据一致,故鉴定化合物Ⅱ为Paxdaphnine A,结构式为:
       2.2.3  化合物Ⅲ
       无色固体。postive ESIMS: m/z: 402 [M + H]+;从1H NMR,13C NMR,DEPT和ESIMS推测分子式为C24H35NO4;由分子式可推测化合物Ⅱ占有8个不饱和度。1H NMR(500 MHz,CDCl3)d (in ppm):0.85 (3H,d,6), 0.93 (3H,d,6), 2.12 (3H,s NMe), 3.70 (3H, s, OMe); 13C NMR(125 MHz,CDCl3)d (in ppm):16.2 (q), 16.8 (q), 21.4 (t), 25.8 (t), 27.7 (t), 27.8 (t), 29.6 (t), 32.8 (d), 35.9 (s), 38.9 (d), 42.0 (t), 43.0 (t), 46.0 (q), 46.3 (s), 50.8 (q), 55.9 (t), 61.7 (t), 62.8 (t), 97.7 (s), 115.8 (s), 149.7 (s), 153.9 (s), 167.0 (s), 169.1 (s)。化合物Ⅲ与文献报道Daphgracine[8]波谱数据一致,故鉴定化合物Ⅲ为Daphgracine,结构式为:
       2.2.4  化合物Ⅳ
       无色固体。postive ESIMS: m/z: 388 [M + H]+;从1H NMR,13C NMR,DEPT和ESIMS推测分子式为C23H33NO4;由分子式可推测化合物Ⅱ占有8个不饱和度。1H NMR(500 MHz,CDCl3)d (in ppm):0.81 (3H,t,7.5), 2.02 (3H,s,NMe), 3.58 (3H,s,OMe); 13C NMR(125 MHz,CDCl3)d (in ppm):7.4 (q), 21.5 (t), 25.8 (t), 27.4 (t), 27.8 (t), 29.7 (t), 32.8 (d), 35.7 (t), 35.9 (s), 42.0 (t), 43.0 (t), 46.0 (q), 46.4 (s), 50.8 (q), 55.9 (t), 61.7 (t), 62.8 (t), 96.2 (s), 115.7 (s), 149.7 (s), 153.9 (s), 167.0 (s), 169.1(s)。化合物Ⅳ与文献报道Daphgraciline[8] 波谱数据一致,故鉴定化合物Ⅳ为Daphgraciline,结构式为:
       2.2.5  化合物Ⅴ
       无色固体。postive ESIMS: m/z: 404[M + H]+;从1H NMR,13C NMR,DEPT和ESIMS推测分子式为C24H37NO4;由分子式可推测化合物Ⅱ占有7个不饱和度。1H NMR(400 MHz,CDCl3)d (in ppm):0.85 (3H,t,7.2), 2.14 (3H,s, NMe), 3.16 (3H,s,OMe), 3.64 (3H,s,OMe); 13C NMR(100 MHz,CDCl3)d (in ppm):7.7 (q), 22.3 (t), 27.2 (t), 27.4 (t), 27.6 (t), 27.9 (t), 28.7 (t), 32.8 (d), 36.3 (d), 39.7 (t), 42.4 (t); 42.5 (d), 46.5 (s), 46.7 (q), 47.1 (q), 51.0 (q), 54.7 (d), 56.2 (t), 61.7 (t), 62.8 (t), 98.9 (s), 133.1 (s), 146.0 (s), 175.3 (s)。化合物Ⅴ与文献报道Yuzurine[9]波谱数据一致,并与Yuzurine的薄层具有相同的Rf值,故鉴定化合物Ⅴ为Yuzurine,结构式为:
        
       3  讨论
       交让木果实乙醇提取物氯仿萃取总碱部分经硅胶柱层析,RP-18反相柱层析,Sephadex LH-20层析,分离得到5个单体化合物,通过理化性质,波谱解析,文献检索等方法确定了化合物Ⅰ~Ⅴ均为虎皮楠生物碱,分别为:Paxdaphnine B (Ⅰ), Paxdaphnine A(Ⅱ), Daphgracine (Ⅲ),Daphgraciline (Ⅳ),Yuzurine (Ⅴ)。其中化合物Ⅰ和化合物Ⅱ为首次从该种植物中分得。本研究为进一步开发利用虎皮楠属植物提供了理论依据。
       【参考文献】
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       [5]Li, ZY; Chen, P; Xu, HG; Yang, YM; Guo, YW etc, Macropodumines D and E, Two New Alkaloids with Unusual Skeletons from Daphniphyllum macropodum Miq, Organic Letter, 2007, 9, 477.
       
       [6]Zhang, W., Guo, Y. W., Krohn, K., Macropodumines A-C: Novel Pentacyclic Alkaloids with an Unusual Skeleton or Zwitterion Moiety from Daphniphyllum macropodum Miq., Chemistry, 2006, 12, 5122.
       
       [7]Fan, C. Q., Yin, S., Xue, J. J., Yue, J.M., Tetrahedron., Novel Alkaloids, Paxdaphnines A and B with Unprecedented Skeletons from The Seeds of Daphniphyllum paxianum, 2007,63,115.
       
       [8]Yamamura,S., Lamberton, J. A., Niwa, M., Endo, K., Hirata, Y., Three New Daphniphyllum Alkaloids With An αβ,γδ-Unsaturated Ester Group From Daphniphyllum gracile Gage,Chem. Lett. 1980, 393.
       
       [9]Yamamura,S, Lamberton, J. A., Irikawa, H., Okumura, Y, Toda, M., Hirata, Y. Bull, Chem.Soc.Jpn. 1977, 50, 1836.

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