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2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2- diazaphosphorine Supported on Polystyrene (PS-BEMP) as an Efficient Recoverable and Reusable Catalyst for the Phenolysis of Epoxides under Solvent-Free Conditions
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 28 SEP 2010 , DOI: 10.1002/adsc.201000375
Artis Zvagulis , Simona Bonollo , Daniela Lanari , Ferdinando Pizzo , Luigi Vaccaro

2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine supported on polystyrene (PS-BEMP) is an efficient catalyst for the ring-opening of epoxides with phenols (1.0 equiv.). Excellent yields have been obtained and in most of the cases the final products have been isolated in pure form without any additional purification step. E-factors associated to this protocol are small and further improvements were obtained by setting a cyclic continuous-flow reactor operating under solvent-free conditions (SolFC) that allowed us to minimize waste and reduce the E-factor by 95% compared to batch conditions. In addition the representative synthesis of a 2,3-dihydrobenzo[1,4]dioxepin-5-one has been realized. Optimization of this process was achieved by setting up an automated multi-step continuous-flow reactor based on a phenolysis process and a subsequent lactonization by thermal treatment of the reaction mixture. 3-Phenoxymethyl-2,3-dihydrobenzo[e][1,4]dioxepin-5-one was isolated in pure form and on a multi-gram scale in a very satisfactory 86% overall yield and an E-factor of 1.47.

中文翻译:

2-叔丁基氨基-2-二乙氨基-1,3-二甲基过氢-1,3,2-二氮杂磷负载在聚苯乙烯(PS-BEMP)上,作为无溶剂条件下环氧乙烷的苯酚脱苯反应的高效可回收和可重复使用的催化剂

2聚苯乙烯(PS-BEMP)上负载的-Butylimino-2-二乙氨基-1,3-二甲基过氢-1,3,2-二氮杂膦是一种有效的催化剂,用于使环氧化物与酚(1.0当量)开环。已经获得了优异的产率,并且在大多数情况下,最终产物已经以纯净的形式分离出来,而无需任何额外的纯化步骤。与该协议相关的E因子很小,并且通过设置在无溶剂条件下运行的循环连续流反应器(SolFC)获得了进一步的改进,这使我们能够最大限度地减少浪费并将E因子与批处理条件相比减少了95% 。另外,已经实现了2,3-二氢苯并[1,4]二氧杂环戊烯-5-酮的代表性合成。通过建立基于酚醛化方法的自动化多步连续流反应器并随后通过反应混合物的热处理进行内酯化来实现此过程的优化。3-Phenoxymethyl-2,3-dihydrobenzo [e [[1,4] dioxepin-5-one)以纯克形式和多克级分离,总收率非常令人满意,为86%,E因子为1.47。
更新日期:2017-01-31
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