钯催化苯酚氧化羰基化合成碳酸二苯酯反应机理的研究进展  

Research Advances in Reaction Mechanism for Pd-Catalyzed Oxidative Carbonylation of Phenol to Diphenyl Carbonate

作　　者：刘敏[1] 吴元欣[1] 杜治平[1] 袁华[1] 戈军伟[1] 

机构地区：[1]武汉工程大学化工与制药学院,湖北省新型反应器与绿色化学工艺重点实验室,湖北武汉430073

出　　处：《催化学报》2008年第5期489-496,共8页

基　　金：国家自然科学基金(20476083)

摘　　要：综述了Pd2+催化苯酚氧化羰基化合成碳酸二苯酯反应机理的最新研究进展,详细介绍了对催化机理的验证和如何实现Pd催化体系的高效循环.苯酚氧化羰基化合成碳酸二苯酯催化机理的研究表明,碳酸二苯酯是通过CO对Pd-O键的插入和中间体Pd(COOPh)(OPh)的还原消除而生成的.在Pd催化剂体系中引入配体和氧化还原助剂,能防止Pd0的聚集,提高Pd0再生为活性Pd2+的速率,加速催化循环.分析总结了Pd催化剂体系目前存在的问题,并提出了催化剂体系的研究方向.Advances in the reaction mechanism for Pd-catalyzed oxidative carbonylation of phenol to diphenyl carbonate were reviewed. The validation of the reaction mechanism and how to realize the efficient recycle of the Pd-catalyzed system were introduced in detail. The catalytic mechanism for the oxidative carbonvlation of phenol to diphenyl carbonate showed that diphenyl carbonate was produced by the insertion of CO into the Pd-O bond and subsequent reductive elimination of intermediate Pd（COOPh）（OPh）. The aggregation of Pd^0 could be reduced and the regeneration rate of active Pd^2＋ from Pd^0 could be improved to accelerate the catalytic recycle by the addition of ligands and redox promoters into the Pd catalyst. The problems existing in the reaction system were summarized, and the direction for research and development of the catalyst system was pointed out.

关 键 词：苯酚 氧化羰基化 碳酸二苯酯 钯 催化剂 反应机理 

分 类 号：O643.12[理学—物理化学]