摘要/Abstract

1,5-苯并二氮杂?类化合物是一类具有重要生物或药理活性的七元氮杂环化合物, 酯基、羧基、酰基、芳基等均是其活性基团. 在室温(25 ℃)下以醛羰基化合物或二羰基化合物、3-丁炔-2-酮、取代的邻苯二胺为原料, 无水乙醇为溶剂, 磁性纳米铁酸钴(CoFe₂O₄)为催化剂/无催化剂条件下三组分串联反应一锅绿色合成34种COR、COOR或COOH取代的1,5-苯并二氮杂?类化合物, 产率最高可达90%, 并提出了催化串联合成反应机理. 该串联反应历经迈克尔加成反应、亲核加成反应、脱水反应、分子内的亚胺-烯胺环合反应、质子转移等反应过程, 一个反应体系内合成了多官能团化的1,5-苯并二氮杂?化合物, 实现了温和条件下, 一个反应体系中在苯并二氮杂?的七元环上同时引入活性的酰基、酯基或羧基等多个活性基团. 该方法的优势在于合成方法新颖、原子经济、目标化合物产率及选择性较高, 实现了反应过程的绿色化, 为绿色合成苯并氮杂?类化合物提供了新思路.
关键词: 三组分串联反应, 绿色合成, 1,5-苯并二氮杂?化合物
1,5-Benzodiazepine compounds are seven-membered nitrogen heterocyclic compounds with important biological and pharmacological activities. Ester group, carboxyl group, acyl group and aryl group are active groups of 1,5-benzodiazepine compounds. One-pot green synthesis of 34 kinds of 1,5-benzodiazepines with COR, COOR or COOH by three-component tandem reaction was performed at room temperature (25 ℃) with a yield of up to 90%. The mechanism of catalytic tandem reaction was proposed. These reactions were achieved by using aldehyde carbonyl compounds or dicarbonyl compounds, 3-butyn-2-one, substituted o-phenylenediamine as raw materials, absolute ethanol as solvent, magnetic nano cobalt ferrite (CoFe₂O₄) was realized under catalyst or without catalyst. The multifunctional 1,5-benzodiazepine compounds were formed via Michael addition reaction, nucleophilic addition-dehydration reaction, intramolecular imine-enamine cyclization and proton transfer processes, which realized that multiple active groups such as active acyl, ester or carboxyl groups were simultaneously introduced into the seven-membered ring of the benzodiazepine in a reaction system under mild conditions. This synthesis method has the advantages of novel synthesis method, atom economy, high yield and selectivity of the target compounds, which realize the green reaction process, and provide a new idea for green synthesis of benzozazepines.
Key words: three-component tandem reaction, green synthesis, 1,5-benzodiazepine compounds


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