【摘要】 合成了49个3,4′/4,3′/3,3′-二取代氮苄叉苯胺化合物,采用循环伏安法测得了其还原电位,并对取代基在还原电位中的影响进行了研究.得到了一个四参数(取代基X的Hammett参数σ（X）、取代基Y的Hammett参数σ（Y）、取代基X的激发态取代基参数σ_CC^ex和交叉相互作用项△σ_CC^ex)的最优回归方程.结果表明含间位取代基的氮苄叉苯胺还原电位中的取代基效应与双对位取代的氮苄叉苯胺还原电位中的取代基效应是不同的.对于3,4′/4,3′/3,3′-二取代氮苄叉苯胺来说,取代基的诱导效应和共轭效应的作用可以合并,所以在回归方程中应用了σ（X）和σ（Y）,另外,取代基X和Y间的交叉相互作用项也起到了重要作用.相比于4,4′-二取代的氮苄叉苯胺,取代基X对3,4′/4,3′/3,3′-二取代氮苄叉苯胺还原电位的贡献要小一些,Y对3,4′/4,3′/3,3′-二取代氮苄叉苯胺还原电位的贡献要大一些.总之,不管是4,4′-二取代氮苄叉苯胺还是3,4′/4,3′/3,3′-二取代氮苄叉苯胺,取代基X对其还原电位的贡献大于Y的贡献.更多还原

【Abstract】 Effects of meta-substituent of 3,4’/4,3’/3,3’-substituted benzylideneanilines（XBAYs） on the electrochemical reduction potentials(E_（Red）) were investigated,in which 49 samples of target compounds were synthesized,and their reduction potentials were measured by cyclic voltammetry.The substituent effects on the E_（Red） of target compounds were analyzed and an optimality equation with four parameters(Hammett constant σ of X,Hammett constant σ of Y,excited-state substituent constant σ_CC^ex of X,and the substituent specific cross-interaction effect △σ_CC^ex2 between X and Y) was obtained.The results show that the factors affecting the E_（Red） of 3,4’/4,3’/3,3’-substituted XBAYs are different from those of4,4’-substituted XBAYs.For 3,474,373,3’-substituted XBAYs,σ（X） and σ（Y） must be employed,and the contribution of △σ_CC^ex2 is important and not negligible.Compared with4,4’-substituted XBAYs,X group contributes less to 3,474,373,3’-substituted XBAYs,while Y group contributes more to them.Additionally,it was observed that either para-substituted XBAYs or meta-substituted XBAYs,the substituent effects of X are larger than those of Y on the E_（Red） of substituted XBAYs.更多还原