Electrochemical study of 4-chloroaniline in a water/acetonitrile mixture. A new method for the synthesis of 4-chloro-2-(phenylsulfonyl)aniline and N-(4-chlorophenyl)benzenesulfonamide?

RSC Advances Pub Date: 2020-08-26 DOI: 10.1039/D0RA05680D

Abstract

The electrochemical oxidation of 4-chloroaniline as a model compound in a water/acetonitrile mixture was investigated by cyclic voltammetry and differential pulse voltammetry. It was established that one-electron oxidation of 4-chloroaniline followed by disproportionation reaction affords unstable (4-iminocyclohexa-2,5-dien-1-ylidene)chloronium. In water/acetonitrile mixtures and in the absence of nucleophiles, the most likely reaction on produced chloronium is hydrolysis and p-quinoneimine formation. The electrochemical oxidation of 4-chloroaniline in the presence of arylsulfinic acids was also investigated in a water/acetonitrile mixture at a glassy carbon electrode. It was established that under these conditions, the anodically generated chloronium reacts with benzenesulfinic acid to produce the corresponding diaryl sulfone and N-phenylbenzenesulfonamide derivatives. In addition, Gaussian 09W was applied for prediction of the possible product by the calculation of natural charge, LUMO orbital energies and thermodynamic stability of intermediates and products.

Graphical abstract: Electrochemical study of 4-chloroaniline in a water/acetonitrile mixture. A new method for the synthesis of 4-chloro-2-(phenylsulfonyl)aniline and N-(4-chlorophenyl)benzenesulfonamide
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