Cu(TFA)_2催化N-甲基芳胺和α-重氮-β-酮酸对硝基苄酯的N—H插入反应研究  

Study on the N-H insertion reaction of N-methyl anilines and 4-nitrobenzyl α-diazo-β-keto-carboxylates under the catalysis of Cu(TFA)_2

作　　者：孙楠[1] 骆佳丽 江晋[2] 胡宝祥[1] 莫卫民[1] 胡信全[1] 

机构地区：[1]浙江工业大学化学工程与材料学院,浙江杭州310032 [2]杭州中美华东制药有限公司,浙江杭州310011

出　　处：《浙江工业大学学报》2014年第1期81-87,共7页Journal of Zhejiang University of Technology

基　　金：浙江省科技厅重大专项资助项目(2010C11039);浙江省重点创新团队资助项目(2009R50002)

摘　　要：研究了金属催化下N-甲基芳胺和α-重氮-β-酮酸对硝基苄酯的N-H插入反应.考察了催化剂的种类,反应介质和催化剂的用量对反应的影响.实验结果表明：Cu（TFA）2对该反应显示出最佳催化性能.最后,在Cu（TFA）2催化下,以甲苯为反应溶剂,回流条件下,快速、高选择性的制备了一系列取代的α-（N-甲基-N-芳基）氨基-β-酮酸对硝基苄酯,分离收率为69％～99％.该方法具有操作简单,催化剂廉价易得,反应时间短,产率普遍较高等特点.An efficient method for the preparation of 4-nitrobenzyl α-（N-methyl-N-aryl）amino-β-keto-carboxylates has been developed from the corresponding N-methyl anilines and 4-nitrobenzyl α-diazo-β-keto-carboxylates via N-H insertion reaction.Cu（TFA）2 exhibited excellent catalytic activity in this reaction.By utilizing Cu（TFA）2 as catalyst and in refluxing toluene,a broad range of substituted N-methyl anilines smoothly reacted with various 4-nitrobenzyl α-diazo-β-ketocarboxylates to form corresponding 4-nitrobenzyl α-（N-methyl-N-aryl）amino-β-keto-carboxylates in high selectivity and the isolated yields were 69％ ～99％.This developed method was facile,efficient and easy to operate.More importantly,the catalyst Cu（TFA）2 was less expensive than traditional rhodium catalysts.

关 键 词：N-甲基苯胺 α-重氮-β-酮酸对硝基苄酯 三氟乙酸酮 N-H插入反应 

分 类 号：O626.4[理学—有机化学]