Nucleophilic Substitution Reaction of p-Dinitrobenzene by a Carbanion: Evidence for Electron Transfer Mechanism  

作　　者：刘有成 张凯东 吕建明 吴隆民 刘中立 

出　　处：《Chinese Journal of Chemistry》2002年第11期1453-1456,1135,共4页中国化学（英文版）

基　　金：theNationalNaturalScienceFoundationofChina (Nos.2 9832 0 40and 2 0 0 72 0 36 )andtheSpecialFundforDoc toralProgramfromtheMinistryofEducationofChina

摘　　要：On the basis of investigation of cyclic voltammetry, EPR spectroscopy and competition experiments, the nucleophilic substitution reaction of p- dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano-α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of p-dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.On the basis of investigation of cyclic voltammetry, EPR spectroscopy and competition experiments, the nucleophilic substitution reaction of p- dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano-α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of p-dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.

关 键 词：single electron transfer p-dinitrobenzene radical anion α-cyanoacetate carbanion retarding effect 

分 类 号：O625[理学—有机化学]