对-(β-羟乙基砜)苯胺的电化学合成  

Electrochemical Synthesis of p-(β-Hydroxyethyl Sulfone)Aniline

作　　者：郭浩 钮东方[1] 胡硕真 张新胜[1] Hao Guo;Dong-Fang Niu;Shuo-Zhen Hu;Xin-Sheng Zhang(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237

出　　处：《电化学》2021年第5期498-507,共10页Journal of Electrochemistry

基　　金：国家重点研发计划项目(No.2017YFB0307502)资助。

摘　　要：本文研究了以对-硝基苯基-β-羟乙基砜为原料在铅板电极上电化学还原制备对-(β-羟乙基砜)苯胺的反应,探究电流密度、通电量、温度和硫酸浓度对电流效率和产率的影响。在最优条件下(电流密度300 A·m^(-2),理论通电量6.0 F·mol^(-1),温度70 ℃,硫酸浓度1.5 mol·L^(-1)),该反应的电流效率达到92.7%,产率达到93.0%。在该最优条件的基础上向电解液中加入质量分数2.0%的硫酸钛可将产率提升至97.8%,硫酸钛的引入间接缓解了反应后期原料扩散速率慢的问题。Para-ester is the most important intermediate for the preparation of ethylene sulfone type reactive dyes,which is usually used in the dyeing of cellulose fibers and synthetic fibers.P-(β-hydroxyethyl sulfone)aniline is an important intermediate for the synthesis of para-ester.In this paper,p-(β-hydroxyethyl sulfone)aniline was prepared by electrochemical method,having the advantages of simple process,mild reaction condition,less environmental pollution,easy reaction control and so on.It has strong development potential and industrial application prospect.The electrochemical reduction of p-nitrophenyl-β-hydroxyethyl sulfone on a lead plate electrode to prepare p-(β-hydroxyethyl sulfone)aniline was investigated,and the reaction was carried out in a two-cell cationic diaphragm electrolytic cell.The electrolysis parameters,such as current density,electricity quantity,temperature and concentration of sulfuric acid,were firstly optimized to achieve a desirable current efficiency and excellent yield of p-(β-Hydroxyethyl Sulfone)Aniline.Under the optimal conditions(current density:300 A·m^(-2),electricity quantity:6.0 F·mol^(-1),temperature:70 ℃,sulfuric acid concentration:1.5 mol·L^(-1)),the current efficiency and yield of the target reaction reached 92.7%and 93.0%,respectively.Moreover,the introduction of 2.0%mass fraction of titanium sulfate additive to the electrolyte could indirectly alleviate the problem of slow diffusion rate of raw material in the late stage of electrolysis,which,in turn,could further increase the yield to 97.8%.At the later stage of reaction,as the concentration of raw materials decreased,the difference between the concentration in the body solution and the electrode surface became smaller,and the diffusion rate of raw materials from the solution to the electrode surface became slower,resulting in a slow reduction reaction rate.After adding titanium sulfate,Ti4+was mainly diffused to the electrode surface in the late reaction solution,and Ti3+with strong reducing property was reduced o

关 键 词：对-硝基苯基-β-羟乙基砜 对-(β-羟乙基砜)苯胺 电化学还原 硫酸钛 

分 类 号：TQ610.1[化学工程—精细化工] TQ246.31