铜催化α,β-不饱和羧酸与三氟碘乙烷或亚磷酸二异丙酯的脱羧偶联反应研究

发布时间：2018-06-01 12:14

本文选题：脱羧偶联反应 + 三氟乙基　；参考：《郑州大学》2017年硕士论文

【摘要】：本论文分为两部分。第一部分主要研究了碘代三氟乙烷与α,β-不饱和羧酸进行的脱羧偶联反应;第二部分研究了亚磷酸二异丙酯与α,β-不饱和羧酸利用脱羧偶联反应来构筑C-P键。1.碘代三氟乙烷与α,β-不饱和羧酸的脱羧偶联反应的研究通过研究碘代三氟乙烷与α,β-不饱和羧酸的脱羧偶联反应,发现了一种简便有效的直接引入三氟乙基的方法。通过对催化剂、配体、溶剂、添加剂、温度、时间的筛选,得到了最佳的反应条件:在氩气保护下以Cu(OTf)2为催化剂,Ag2CO3为添加物,Et3N作为碱,DMSO作溶剂。以α,β-不饱和羧酸为底物,油浴80oC反应24 h(Scheme 1)。并在上述最佳条件下,研究了一系列的α,β-不饱和羧酸与碘代三氟乙烷的脱羧偶联反应活性,结果显示大多数α,β-不饱和羧酸衍生物均得到了中等到较高的收率。2.亚磷酸二异丙酯与α,β-不饱和羧酸进行的脱羧偶联反应的研究通过研究亚磷酸二异丙酯与α,β-不饱和羧酸进行的脱羧偶联反应,发现了一种简便有效的构筑C-P键的方法。通过对催化剂、配体、溶剂、添加剂、温度、时间的筛选,得到了最佳的反应条件:在氩气保护下,以Cu CO3为催化剂,1,10-phen为配体,Ag2O为添加物,DMSO作溶剂。以α,β-不饱和羧酸为底物,在油浴110oC反应12 h(Scheme 2)。在最佳反应条件下,研究了一系列的α,β-不饱和羧酸与亚磷酸二异丙酯的脱羧偶联反应活性。
[Abstract]:This paper is divided into two parts. The first part mainly studies the decarboxylation coupling reaction between iodide three fluoroethane and alpha, beta unsaturated carboxylic acid. The second part studies the preparation of C-P bond.1. iodide three fluoroethane and alpha, beta unsaturated carboxylic acid by decarboxylation coupling reaction of alpha and beta unsaturated carboxylic acid. Through the study of decarboxylation of three fluoroethane with alpha, beta unsaturated carboxylic acid, a simple and effective method to direct the introduction of three fluoroethyl was found. The optimum reaction conditions were obtained by screening the catalyst, ligand, solvent, additive, temperature and time. Cu (OTf) 2 was used as catalyst and Ag2CO3 was added under the protection of argon. Et3N is used as a base, DMSO as a solvent. With alpha, beta unsaturated carboxylic acid as the substrate and oil bath 80oC reaction 24 h (Scheme 1), the decarboxylic coupling reaction activity of a series of alpha, beta unsaturated carboxylic acids and iodinated three fluoroethane is studied under the above optimum conditions. The results show that most of the alpha, beta unsaturated carboxylic acid derivatives have been medium to high. The decarboxylation of.2. phosphoric acid two isopropyl ester with alpha, beta unsaturated carboxylic acid has been studied by the decarboxylation coupling reaction of two isopropyl phosphite with alpha, beta unsaturated carboxylic acid, and a simple and effective method to construct the C-P bond was found. Under the optimum reaction conditions, a series of decarboxylic coupling reactions of alpha, beta unsaturated carboxylic acids and two isopropyl phosphite were studied under the optimum reaction conditions, with Cu CO3 as the catalyst, 1,10-phen as the ligand, Ag2O as the ligand, the DMSO as the solvent, the alpha, beta unsaturated carboxylic acid as the substrate and the oil bath 110oC reaction 12 h (Scheme 2) under the optimum reaction conditions. Activity.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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