朝鲜白头翁的化学成分研究

【作者】 关颖丽；

【导师】 许永男；

【作者基本信息】 沈阳药科大学 ， 中药化学， 2008， 硕士

【摘要】 朝鲜白头翁Pulsatilla cernua(Thunb．)Bercht et Opiz．来源于毛茛科(Ranunculaceae)植物，主要分布于我国吉林、辽宁、黑龙江等地区。具有清热解毒、凉血止痢的功效。现代研究表明，朝鲜白头翁中化学成分有着很强的生物活性，尤其是发现某些活性成分在治疗老年性痴呆(阿尔茨海默病，Alzheimer’s disease，AD)效果显著。本文对其50％乙醇提取物进行化学成分的研究，经分步溶剂萃取法、大孔吸附树脂柱色谱、硅胶柱色谱、薄层色谱、循环制备高效液相色谱等方法从中提取分离出17个单体化合物。经理化性质及波谱解析鉴定，并与参考文献对照，确定其中1个为新化合物，1个为首次从该属植物分离得到，2个为首次从该植物分离得到。新化合物的结构为：齐墩果酸3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(17)。首次从该属植物分离的化合物结构分别为：齐墩果酸28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(3)。首次从该植物分离的化合物结构分别为：齐墩果酸3-D-β-D-P比喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(6)；常春藤皂苷元28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(7)。其它已知化合物结构分别为：齐墩果酸3-O-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(1)；常春藤皂苷元3-O-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(2)；常春藤皂苷元3-O-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(4)；齐墩果酸3-O-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖苷(5)；齐墩果酸3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(8)；齐墩果酸3-O-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(9)；常春藤皂苷元3-O-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(10)；常春藤皂苷元3-O-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(11)；常春藤皂苷元3-O-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(12)；齐墩果酸3-O-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(13)；齐墩果酸3-O-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(14)；齐墩果酸3-D-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖酯苷(15)；常春藤皂苷元3-O-β-D-吡喃葡萄糖基(1→3)-α-L-吡喃鼠李糖基(1→2)[β-D-吡喃葡萄糖基(1→4)]-α-L-吡喃阿拉伯糖基-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-P比喃葡萄糖酯苷(16)。更多还原

【Abstract】 Pulsatilla cernua (Thunb.) Bercht et Opiz., belonging to Ranunculaceae, mainly distributed in Jilin, Liaoning, Heilongjiang and other regions of China, with its effect of expelling toxin by cooling, and cooling blood to stop bleeding. Modern researches showed that the chemical composition of Pulsatilla cernua have strong biological activities. Especially some active components have remarkable effect in treatment of Alzheimer’s disease. In the article, the chemical constituents in the 50% alcohol extract of Pulsatilla cernua were studied, and solvent extraction, macroporous adsorptive resins, open silica gel column chromatograph, TLC, recycling preparative HPLC and other methods were used. 17 compouds were isolated and identified by spectral analysis. One was a new compound, one compound was isolated from this genus for the first time, and two compounds were isolated from this species for the first time.Structure of a new compound: oleanolic acid 3-O-β-D-glucopyranosyl(1→4)-β-D-glucopyranosyl(1→3)-p-L-rharnnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosylester (17).Structure of a compound from Pulsatilla for the first time: oleanolic acid 28-O -α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (3).Structures of two compounds from Pulsatilla cernua for the first time: oleanolic acid 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranoside (6); hederagenin 28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosylester (7).Structures of others: oleanolic acid 3-O-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranoside(1); hederagenin 3-O-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranoside (2); hederagenin 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranoside(4); oleanolic acid 3-O-α-L-rhamnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranoside (5); oleanolic acid 3-O-β-D-glucopyranosyl(1→4)-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranoside (8); oleanolic acid 3-O-α -L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (9); hederagenin 3-O-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl (1→6)-β-D-glucopyranosyl ester (10); hederagenin 3-O-α-L-rhamnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (11); hederagenin 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyransyl(1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (12); oleanolic acid 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (13); oleanolic acid 3-O-α-L-rhamnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (14); oleanolic acid 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (15); hederagenin 3-O-β-D-glucopyranosyl (1→3)-α-L-rhamnopyranosyl(1→2)[β-D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester (16).更多还原