摘要/Abstract

以取代的邻苯二胺、1,3-环戊二酮或1,3-环己二酮(5,5-二甲基-1,3-环己二酮)、2,3-二羰基化合物为原料, 无水乙醇为溶剂, 对甲苯磺酸为催化剂, 经2~5 h串联反应一锅合成43种新颖的1,5-苯并二氮杂?化合物, 产率最高可达95%. 该反应序列首先通过两次的亲核加成-脱水反应过程, 形成分子内亚胺和烯胺结构的活性中间体, 然后再经分子内的碳碳偶联环合-质子转移等过程, 生成多环稠合的1,5-苯并二氮杂?目标化合物, 实现了在一个反应体系中形成一个二氮杂七元环和四个新化学键(两个C—N, 一个C=C, 一个C—C). 该方法操作简单, 反应便捷, 对环境友好, 产率高, 为1,5-苯并二氮杂?化合物的合成提供绿色环保, 高效简便的合成思路.
关键词: 1,5-苯并二氮杂?类化合物, 串联反应, 绿色合成, 机理
43 novel 1,5-benzodiazepine compounds were obtained via one-pot multicomponent and tadem reactions for 2~5 h and the yield of the target compounds is up to 95%. These reactions were achieved by reacting substituted 1,2-phenylene- diamines, 1,3-cyclopentanedione or 1,3-cyclohexanedione (5,5-dimethyl-1,3-cyclohexanedione), 2,3-dicarbonyl compounds with p-toluenesulfonic acid as catalyst in EtOH. The active intermediates with the imine and enamine structures in the molecule were formed by two nucleophilic addition-dehydration processes and then 1,5-benzodiazepine compounds were obtained via carbon-carbon coupling cyclization and proton transfer processes, which realized the construction of one new seven- membered ring and four new chemical bonds (two C—N, one C=C, one C—C) in one-pot. It provides a green, environmentally friendly, efficient and simple synthetic thought for the synthesis of 1,5-benzodiazepine compounds.
Key words: 1,5-benzodiazepine compound, tadem reaction, green synthesis, mechanism


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