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通关藤和多刺绿绒蒿的化学成分研究
Studies on the Chemical Constituents from Marsdenia Tenacissima and Meconopsis Horridula
【作者】 李启发;
【导师】 王晓玲;
【作者基本信息】 西南民族大学 , 有机化学, 2007, 硕士
【摘要】 本论文由三部分组成,第一、二部分为实验论文,分别报道了摩萝科牛奶菜属植物通关藤和罂粟科绿绒蒿属多刺绿绒蒿的化学成分研究结果。第三部分概述了通关藤化学成分及药理活性研究进展。第一部分为通关藤的化学成分研究,内容包括二章。第一章主要报道云南传统药用植物通关藤茎的化学成分研究,从该植物中共分离纯化出22个化合物,运用ESI-MS、1H-NMR、13C-NMR、DEPT、HMBC、HSQC、NOESY以及X-Ray等现代波谱技术并结合化学方法,鉴定出21个化合物,其中9个为独特C21甾体环氧孕甾烷:11α, 12β-二-丁烯酰-通关藤苷元B(1),通关藤苷E(2),通关藤苷F(3),通关藤苷G(4),通关藤苷H(5),通关藤苷I(6),通关藤苷J(7),11α, 12β-丙酮缩二羟基-通关藤苷元B(8),tenacissoside C(9);两个木脂素:1-(4-羟基-3-甲氧基-苯基)-2-{2-甲氧基-4-[1-(E)-丙稀-3-醇]-苯氧基}-丙烷-1,3-二醇(赤式)(10), (?)-松脂素(11);一个香豆素:东莨菪素(12);一个有机酸:丁二酸(13),一个还原糖:半乳糖醇(15),两个双糖:Marsectobiose(14),苦绳双糖苷(16);一个神经酰胺:Poke-weed Cerebroside(17);一个C30的甾体化合物:4-Methylstigmasta-7,24(28)-dien-3-ol(18)以及牛弥菜醇(19),β-谷甾醇(20)和胡萝卜苷(21)。其中(1)?(7)为新化物,并通过X-射线单晶衍射确定了化合物7的绝对构型,(10)、(17)和(18)为首次从该属中分离得到,11?16为首次从该植物中分离得到。第二章报道了通关藤的挥发性化学成分,采用气相色谱-质谱(GC-MS)联用方法对云南产通关藤药材的挥发油成分进行分析,共分离出90余个峰,通过质谱检索与标准图库对照和分析,并参考相应的保留时间确定了其中的62个组分,它们的相对含量占总挥发油的94.9 %。其中含量最大的是棕榈酸(32.08 %),其次有5-ethenyltetrahy-2-Furanmethanol (8.13 %)、橙花叔醇(6.31 %)、油酸酰胺(3.59 %)、2,4-癸二烯醛(2.74 %)、白昌考烯(2.72 %)、6-(1,1-二甲基-3-丁烯基)-3-甲基-二氢吡喃(2.14 %)等。第二部分为藏药多刺绿绒蒿的化学成分研究。从该种植物中共分离得到7个化合物。通过ESI-MS,1H, 13C-NMR等各种现代波谱技术,鉴定出3个生物碱:原阿片碱(22),华紫堇碱(23),(+)-Des-N-methylcryprochine(24)和4个黄酮:4’, 5, 7-三羟基-3’, 5’-二甲氧基黄酮(25),木犀草素(26),芹菜素(27),大风子素(28)。(22),(23)和(25)-(28)首次从该植物分离得到,(24)为新化合物。第三部分综述通关藤近年来的研究成果,包括其化学成分及药理活性两个方面,列举了从该药用植物中分离得到的53个化合物,同时也对其主要次生代谢物的药理学和生物活性进行了总结。
【Abstract】 This dissertation consists of three parts. The first and second parts elaborate the phytochemical investigation of two medicinal plants of Marsdenia tenacissima and Meconopsis horridula Hook .f. et. Thoms. The third part reviewed the chemical constituents and bioactive studied of M. tenacissima.The stems of M. tenacissima, popularly known as‘Tong-guang-teng’, is widely employed to treat inflammation, asthma and cancer in southwest of China. In clinic, the preparations from the aqueous extract of the stems of M. tenacissima, has been used for treatment of gastric carcinoma and liver cancer. The first chapter is about the chemical constituents isolated from stems of M. tenacissima. 22 compounds were isolated and their structures were determined by 1D, 2D-NMR and X-Ray analysis and chemical evidence. 9 compounds were elucidated as peculiarity polyoxypregnane: 11α,12β-Di-O-tigloyl-tenacigenin B (1), tenacigenoside E (2), tenacigenoside F (3), tenacigenoside G (4), tenacigenoside H (5), tenacigenoside I (6), tenacigenoside J (7), 11α-12β-Acetonide-tenacigenin B (8), tenacissoside C (9). The other compounds were identified as 1-(4-hydroxy-3-methoxyphenyl)- 2-{2-methoxy-4-[1-(E)-propen-3-ol]-phenoxy}-propan-1,3-diol (erythro) (10), (?)- pinoresinol (11), scopoletin (12), amber acid (13), D-galactitol (15), marsectobiose (14), methylβ-D-theveropyranosyl-(1→4)-β-D-cymaropyranoside (16), poke-weed Cerebroside (17), 4-Methylstigmasta-7,24(28)-dien-3-ol (18), conduritol (19),β-sitosterol (20), daucosterol (21). Among them, compounds 1?7 were identified as new polyoxypregnanes and absolute configuration of 7 was confirmed by X-Ray experiment. 10, 17 and 18 were isolated from the Marsdenia species for the first time and 11?16 were isolated from the title plant for the first time.Chapter 2 is about the chemical components of essential oil from the stems of M. tenacissima investigated by GC/MS method. More than 90 peaks were separated and 62 components were identified accounting for more than 94.9 % of total essential oil contents. Among them, the main compounds were Palmitic acid (32.08 %), 5-ethenyltetrahy-2-Furanmethanol (8.13 %), Nerlidol (6.31 %), Oleamide (3.59 %), 2,4-Decadienal (2.74 %), Calacorene (2.72 %) and 6-(1,1-dimethyl-3-butenyl)- 3-methyl-dihydro-Pyran (2.14 %).The second part is about the constituents of Meconopsis horridula Hook .f. et. Thoms, an endemic plant mainly distributed in Tibet of China, which is used as a folk medicine for treatment of asthma, lingering dysentery and anal prolapse. Previous researched on this species have found that they mainly contain alkaloids. Our research on this plant identified three alkaloids: (+)-Des-N-methylcryprochine (24), protonine (22), cheilanthifoline (23) and four flavones: tricin (25), luteolin (26), apigenin (27), hydnocarpin (28). Among them, (24) was a new alkaloid and the other was isolated from this plant for the first time.The third part is a review of M. tenacissima, 53 compounds were enumerated, their pharmacology and biologic activities were summarized also.
【Key words】 Tibet medicinal plant; Marsdenia tenacissima; meconopsis horridula; tenacigenoside E-J; (+)-Des-N-methylcryprochine; GC-MS;