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Substituent Effects on Reduction Potentials of Meta-substituted and Para-substituted Benzylideneanilines
Lin-yan Wang,Chao-tun Cao,Chen-zhong Cao
Author NameAffiliationE-mail
Lin-yan Wang School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hu-nan Provincial University Key Laboratory of QSAR/QSPR, Hunan University of Science and Technology, Xiangtan 411201, China  
Chao-tun Cao School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hu-nan Provincial University Key Laboratory of QSAR/QSPR, Hunan University of Science and Technology, Xiangtan 411201, China  
Chen-zhong Cao School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China;Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hu-nan Provincial University Key Laboratory of QSAR/QSPR, Hunan University of Science and Technology, Xiangtan 411201, China czcao@hnust.edu.cn 
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 σCCex of X, and the substituent specific cross-interaction effect ΔσCCex2 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 of 4,4'-substituted XBAYs. For 3,4'/4,3'/3,3'-substituted XBAYs, σ(X) and σ(Y) must be employed, and the contribution of ΔσCCex2 is important and not negligible. Compared with 4,4'-substituted XBAYs, X group contributes less to 3,4'/4,3'/3,3'-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.
Key words:  3,4'/4,3'/3,3'-substituted benzylideneanilines  Substituent effects  Electrochemical reduction potentials  Cyclic voltammetry  Excited-state substituent constant
FundProject:This work was supported by the National Natural Science Foundation of China (No.21272063), the Scientific Research Fund of Hunan Provincial Education Department (No.14C0466), and the Natural Science Foundation of Hunan (No.14JJ3112).
间位取代与双对位取代氮苄叉苯胺还原电位中取代基效应
王琳艳,曹朝暾,曹晨忠
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σCCex和交叉相互作用项ΔσCCex)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.
关键词:  3,4'/4,3'/3,3'-二取代氮苄叉苯胺  取代基效应  还原电位  循环伏安法  激发态取代基参数
DOI:10.1063/1674-0068/29/cjcp1508173
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