三叶悬钩子和棠梨枝叶的化学成分及顺反苯丙烯酸衍生物的转化研究

发布时间：2018-05-18 19:09

本文选题：蔷薇科 + 三叶悬钩子　；参考：《云南大学》2016年博士论文

【摘要】：蔷薇科(Rosaceae)约有124属3300余种,分布于全世界,北温带较多。我国约有51属1000余种,产于全国各地。本研究从蔷薇科植物三叶悬钩子(Rubus delavayi)和棠梨枝叶(Pyrus pashia)中分离出141个化合物,包括16个新化合物,并对部分化合物进行了细胞毒活性、抗氧化作用研究。同时,在植物化学的研究基础上,使用催化量的碘将顺式苯丙烯酸衍生物彻底转化成其反式异构体,建立了简便可靠的转化方法。最后,综述了苯丙烯酸衍生物的结构类型和生物活性,以及顺式、反式苯丙烯酸衍生物相互转化方法的研究进展。三叶悬钩子(R. delavayi)为蔷薇科(Rosaceae)悬钩子属(Rubus)植物,是云南省特有的植物。三叶悬钩子是傈僳族、怒族的常用药,也常用来泡茶,可用于治疗扁桃体炎,感冒,急性结膜炎,痢疾,疮疡,风湿性关节炎等。该植物生长于1600-3000 m地带的山坡沟谷稀疏灌木丛中,在云南主要分布在大理州的弥渡、巍山、剑川、洱源、漾濞等县。研究表明三叶悬钩子的提取物具有抗炎、抗肿瘤、免疫增强等作用。本文利用常规的分离技术,从三叶悬钩子的甲醇提取物中分离、鉴定出单萜类、倍半萜类、三萜类、甾体类、苯丙素类、酚酸类等天然产物,共计75个,包括11个新化合物。化合物59-61是从悬钩子属植物中首次发现的含溴天然产物。棠梨(P. pashia)是蔷薇科(Rosaceae)梨属(Pyrus)的一种植物。棠梨在民间应用广泛,棠梨果树常用作人工栽培梨的砧木；棠梨的花是云南人民喜爱的一道菜肴,它具有降血脂和清理肠胃的作用；棠梨的果实用于治疗咳嗽,泻痢等病症。棠梨的枝叶用于治疗反胃吐食,霍乱吐泻,转筋腹痛等病症。在团队从棠梨的花和枝叶中已分离、鉴定了47个化合物的基础上,本研究进一步研究棠梨枝叶的化学成分,共分离、鉴定出66个化合物,包括5个新化合物,其中(4α)-3-(5,5-dimethyltetrahydrofuranyl)-1-buten-3-ol 3-O-β-D-glucopyranoside (1)和(4β)-3-(5,5-dimethyltetrahydrofuranyl)-1-buten-3-ol 3-O-β-D-glucopyranoside (2)是首次从梨属(Pyrus)中分离到的单萜类化合物。苯丙烯酸衍生物含有C6-C3结构单元,是一类广泛存在于植物中的化学成分,也是医药、化工中的常用中间体和底物。反式苯丙烯酸衍生物的光学异构化现象为顺式和反式异构体的分离、结构鉴定以及后续研究带来较大的麻烦。本文基于从棠梨枝叶中分离到苯丙烯酸衍生物,系统地研究了反式苯丙烯酸衍生物光学异构的特点。探索并建立了将顺式苯丙烯酸衍生物彻底转化成反式异构体的方法,同时还探讨了转化机理。最后,本文归纳和总结了苯丙烯酸衍生物的结构类型及其生物活性,综述了顺式和反式苯丙烯酸衍生物之间转化的方法,并探讨了苯丙烯酸衍生物的研究方向和值得注意的问题。
[Abstract]:There are more than 3300 species belonging to 124 genera of Rosaceae, which are distributed all over the world and are abundant in the northern temperate zone. China has about 51 genera more than 1000 species, produced in all parts of the country. In this study, 141 compounds, including 16 new compounds, were isolated from Rubus delavayi and Pyrus pashia. The cytotoxic activity and antioxidant activity of some compounds were studied. At the same time, based on the study of phytochemistry, a simple and reliable conversion method was established by using the catalytic amount of iodine to completely transform the cis-benzoic acid derivative into its trans-isomer. In the end, the structure and bioactivity of the derivatives were reviewed, and the research progress in the mutual conversion of cis-and trans-acroleic acid derivatives was also reviewed. Rhizoma delavayi, a species of the genus Rubusa (Rosaceaeae), is endemic to Yunnan Province. Trifolium Rubus is a common medicine for Lisu, Nu nationality, also used to make tea, can be used to treat tonsillitis, cold, acute conjunctivitis, dysentery, sore, rheumatoid arthritis and so on. The plant grows in sparse shrub of mountain slope and valley in 1600-3000 m area, and is mainly distributed in Midu, Weishan, Jianchuan, Eryuan and Yangbi counties of Dali Prefecture in Yunnan Province. The results showed that the extract of Rubus trifolium had anti-inflammatory, anti-tumor and immune enhancement effects. In this paper, natural products such as monoterpenoids, sesquiterpenes, triterpenoids, steroids, phenylpropanoids and phenolic acids were isolated from methanol extract of Rubus trifoliata by conventional separation technique. The natural products were 75, including 11 new compounds. Compound 59-61 is the first bromine-containing natural product found in Rubus. P. pashia is a plant of Rosaceaeae (Pyrus). Tang pear is widely used in folk society, and its fruit tree is often used as the rootstock of cultivated pear. The flower of Tang pear is a favorite dish of Yunnan people, it has the function of lowering blood lipid and clearing the stomach, and the fruit of Tang pear is used to treat cough, diarrhea and other diseases. The branches and leaves of Tang pear are used to treat nausea, diarrhea, abdominal pain and so on. On the basis of 47 compounds isolated from the flower and branches and leaves of the pear, the chemical constituents of the leaves and branches of the pear were further studied. A total of 66 compounds, including 5 new compounds, were identified. The monoterpenoid compounds were isolated from Pyrus for the first time, including 4 伪 -tetrohydrofuranyltry-1-buten-3-ol 3-O- 尾 -D-glucopyranoside 1) and 4 尾 -bu-5-dimethyltetrahydrofuranylton-1-buten-3-ol 3-O- 尾 -D-glucopyranoside 2), which were isolated from Pyrus for the first time. Propenoic acid derivatives contain C6-C3 structural units. They are a class of chemical constituents widely found in plants, and are also commonly used as intermediates and substrates in medicine and chemical industry. The phenomenon of optical isomerization of trans-phenylpropenoic acid derivatives is the separation of cis-trans isomers, structural identification and follow-up studies. Based on the separation of phenylacrylic acid derivatives from the branches and leaves of Tangli pear, the characteristics of optical isomerization of trans acroleic acid derivatives were studied systematically. The method of transforming cis-phenylacrylic acid derivatives into trans isomers was established and the conversion mechanism was also discussed. Finally, the structural types and biological activities of the derivatives were summarized, and the methods of conversion between cis-and trans-propionic acid derivatives were reviewed. The research direction and noticeable problems of phenylacryloic acid derivatives are also discussed.
【学位授予单位】：云南大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：Q946

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