基于氰基的过渡金属催化串联反应合成取代喹啉-2,4-二酮研究

发布时间：2018-04-22 17:11

本文选题：过渡金属催化 + 自由基　；参考：《昆明理工大学》2017年硕士论文

【摘要】：过渡金属催化的串联反应已被广泛应用于各类复杂有机化合物的合成。目前已经发展了许多以芳基丙烯酰胺类化合物为原料的过渡金属催化的自由基串联反应,但产物均局限于氧化吲哚,还未见有利用该类底物构建取代喹啉-2,4-二酮类化合物的工作。本论文详细介绍了在此结构上建立的基于氰基的自由基串联反应构建取代的喹啉-2,4-二酮类化合物的研究。论文包含以下三个部分:一、对近年来基于芳基丙烯酰胺类化合物的氧化自由基串联反应进行综述,内容按引入的自由基类型进行分类介绍。二、研究了利用过渡金属催化自由基串联反应构建磷取代喹啉-2,4-二酮类化合物的方法。我们在芳基丙烯酰胺类化合物的基础上,引入氰基反应位点,设计了一类邻氰基芳基丙烯酰胺类化合物。以此为反应底物,用二苯基磷氧或亚磷酸二乙酯为磷源,在硝酸银/六水合硝酸镁催化体系下一步构建了 C-P键、C-C键和C-O双键,高效合成了磷取代喹啉-2,4-二酮类化合物。同时,对反应的普适性与机理进行探究。三、对自由基串联反应构建羰基取代喹啉-2,4-二酮类化合物进行了研究。利用α-酮酸脱羧、醛脱氢、取代的甲基醇氧化脱氢等方式产生酰基自由基,与邻氰基芳基丙烯酰胺反应合成羰基基取代喹啉-2,4-二酮类化合物。建立了三种不同的反应体系:α-酮酸/硝酸银/过二硫酸铵体系;醛/过二硫酸钾体系;取代的甲基醇/氯化亚铁/叔丁基过氧化氢体系;高效构建了羰基取代喹啉-2,4-二酮类化合物。并对反应的普适性与机理分别进行探究。
[Abstract]:The series reaction catalyzed by transition metals has been widely used in the synthesis of various complex organic compounds. At present, a series of free radical series reaction catalyzed by transition metal catalyzed by aryl acrylamide has been developed, but the products are limited to the oxidation of indole, and the construction of the substituted quinoline -2,4- two ketones by using this kind of substrate has not been found. In this paper, the study on the construction of the substituted quinoline -2,4- two ketones based on the cyanyl radical series reaction was introduced in this paper. The thesis contains the following three parts: first, a review of the oxygen free radical series reaction based on aryl amide compounds in recent years is reviewed. The types of free radical are classified. Two, a method for the construction of phosphorus substituted quinoline -2,4- two ketones using transition metal catalyzed free radical series reaction was studied. On the basis of aryl acrylamide compounds, we introduced cyanyl reaction sites and designed a class of adjacent cyanoaryl amide derivatives. Substrate, using two phenyl phosphor oxygen or two ethyl phosphite as the phosphorus source, the C-P bond, C-C bond and C-O double bond were constructed under the catalytic system of silver nitrate / six hydrated magnesium nitrate. The phosphorous substituted quinoline -2,4- two ketones were synthesized efficiently. At the same time, the universality and mechanism of the reaction were investigated. Three, the carbonyl substituted quinoline was constructed for the free radical series reaction. -2,4- two ketones were studied. Acyl radicals were produced by using alpha ketoacid decarboxylation, aldehyde dehydrogenation, substituted methyl alcohol oxidative dehydrogenation and other ways to synthesize carbonyl substituted quinoline -2,4- two ketones. Three different reaction systems were established: alpha ketoacid / silver nitrate / over two ammonium sulfate. The system, aldehyde / two potassium sulphate system, substituted methyl alcohol / ferrous chloride / tert butyl hydrogen peroxide system, and efficient construction of carbonyl substituted quinoline -2,4- two ketones, and explore the universality and mechanism of the reaction respectively.

【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.323

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