Page 130 - 201812

第 35 卷第 12 期 精 细 化 工 Vol.35, No.12
2018 年 12 月 FINE CHEMICALS Dec. 2018

有机电化学与工业
有机媒质作用下芳香醛的间接电合成

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张安伦，曹志成，刘建超，廖艳梅，朱英红
（浙江工业大学 化学工程学院，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1 mmol/L
P 作用下，加入 10%（体积分数，以总体积计）H 2 O，1.2 V 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，1.3 V 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；有机电化学与工业
中图分类号：O646 文献标识码：A 文章编号：1003-5214 (2018) 12-2098-07

Indirect Electro-oxidation Synthesis of Aromatic Aldehyde
Under Organic Mediators

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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 nitro-containing organic mediators including arylimidazole (M), triphenylamine
(P) and carbazole (C) frameworks were synthesized and their electrochemical properties were characterized
using cyclic voltammetry (CV). The oxidation-reduction potentials and electrochemical reversibility of the
organic mediators were greatly effected by their frameworks. The electro-catalytic oxidation activities of
compounds P and C for p-methoxytoluene (p-MT) were investigated by CV and controlled potential
electrolysis at room temperature. The results showed that when the water volume fraction was 10% of the
total volume, p-MT could convert into p-methoxybenzaldehyde (p-MBA) with a yield of 83% in the
presence of 1 mmol/L compound P at 1.2 V. The electro-catalytic activities of compounds P and C for
p-methoxybenzyl alcohol (p-MBzOH) were also investigated. Compound P showed excellent electro-
catalytic activity and selectivity for p-MBzOH, the yield of p-MBA reached 90% through electro-oxidation
at room temperature and at 1.3 V. 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 oxidation-reduction potential
was suitable for the electro-oxidation of p-MT with lower oxidation potential, while C with higher
oxidation-reduction potential was suitable for the electro-oxidation of p-MBzOH with higher oxidation
potential.
Key words: aromatic aldehyde; organic mediator; indirect electro-oxidation; selective electro-oxidation;
reversibility; electro-organic chemisitry and industry
Foundation items: 973 Project from the Ministry of Science and Technology of China (2012CB722604);
National Key Research and Development Program of China (2017YFB0307503)

收稿日期：2018-02-13; 定用日期：2018-05-10; DOI: 10.13550/j.jxhg.20180120
基金项目：973 前期研究项目（2012CB722604）；国家重点研发计划项目（2017YFB0307503）
作者简介： 张安伦（1991—），男，硕士生，E-mail：977823619@qq.com。联系人：朱英红（1975—），女，副教授，E-mail：yhzhuchem@zjut.edu.cn。