Oxidative transformation of N-substituted 3-aminopyrazoles to azopyrazoles using electrogenerated bromine as a mediator

Abstract

The one-pot process of anodic transformation of N-alkyl-3-aminopyrazoles into azopyrazoles under conditions of membraneless electrolysis in an aqueous solution of NaBr was studied for the first time. It was found that under these conditions the aminopyrazoles, which do not have a substituent at position 4, transform into the corresponding 4,4´-dibromoazopyrazoles. The corresponding yield was in the interval of 28—80%, depending on the structure of the products. The transformation of 4-substituted aminopyrazoles resulted in the formation of azopyrazoles in the yields lying within 62—86% when this process was implemented under conditions with the anodically generated Br₂ acting as a mediator. A convenient method of anodic synthesis of azopyrazoles in an aqueous medium without the use of additives of chemical oxidants was proposed. The process is environmentally sound and is characterized by a high atom efficiency (>85%).