有机媒质作用下芳香醛的间接电合成.doc

有机媒质作用下芳香醛的间接电合成 张安伦，曹志成，刘建超，廖艳梅，朱英红* (浙江工业大学 化工学院，浙江 杭州 310032) 摘要：合成了含硝基的芳基咪唑（M）、三苯胺（P）和咔唑（C）3种有机媒质，通过循环伏安法（CV）测试了这3种有机媒质的电化学性能，发现不同的有机框架对媒质的氧化还原电位和电化学可逆性有很大的影响。在室温下通过CV和恒电位电解测试考察了P和C 对对甲氧基甲苯（p-MT）的电催化氧化性能，结果显示：在1mmol/L的P作用下，加入10%(体积分数，以总体积计)H2O，1.2V下，p-MT电化学氧化成对甲氧基苯甲醛（p-MBA）的产率可达83%。而对氧化电位较高的对甲氧基苯甲醇（p-MBzOH）电催化氧化成p-MBA，P也表现出很好电催化活性和选择性，在室温下，1.3V时，p-MBA的产率达90% 。通过P和C分别对p-MT和p-MBzOH选择性电氧化为p-MBA的电催化性能对比，结果显示：氧化还原电位较低的P适合于具有较低氧化电位的p-MT，而氧化还原电位较高的C更适合于具有较高氧化电位的p-MBzOH。 关键词：芳香醛；有机媒质；间接电氧化；选择性电氧化；氧化还原可逆性 中图分类号： O646 文献标识码： 文章编号： Indirect Electro-synthesis of Aromatic Aldehyde Under Organic Mediators ZHANG An-lun, CAO Zhi-cheng, LIU Jian-chao, LIAO Yan-mei, ZHU Ying-hong* （College of chemical engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang,China） Abstract: Three kinds of organic mediators based on arylimidazole (M), triphenylamine (P) and carbazole (C) were synthesized and their electrochemical redox reversibility were characterized through cyclic voltammetry (CV). Their redox potentials and electrochemical reversibility were greatly effected by the organic framework of the mediator. The electro-oxidation activity of p-methoxytoluene (p-MT) under P and C, respectively, were studied through CV and controlled potential electrolysis at room temperature. When 10% H2O (volume ratio) was added, the yield of p-methoxybenzaldehyde (p-MBA) was 83% on the electro-oxidation of p-MT under 1mmol/L P at 1.2V. And the excellent electro-catalytic activity and selectivity of P on the electro-oxidation of p-methoxybenzyl alcohol  (p-MBzOH) to p-MBA were showed, and the yield of p-MBA was 90% at 1.3V. Compared the activity of P and C on the electro-oxidation of p-MT and p-MBzOH, respectively, selectively converting them to p-MBA, P with lower redox potential was suit for the electro-oxidation of p-MT with lower oxidation potential, while C with higher redox potential was suit for the electro-oxidation of p-MBzOH with higher oxidation poten