Outstandingly robust anodic dehydrogenative aniline coupling reaction

Oxidative treatment of anilines usually leads to the formation of black polymers, often referred to as aniline black. This over-oxidation is hardly controllable and also a challenging task in the anodic conversion of anilines. Here, a quick and efficient access to valuable building blocks by anodic cross- and homo-coupling of aniline and benzidine derivatives is reported. This electrosynthesis is easily performed in a simple undivided cell using constant current conditions. The key to the observed outstanding performance and robustness of this system is attributed to the used solvent 1,1,1,3,3,3-hexafluoroisopropanol. The extraordinary performance over a broad range of current density is unprecedented for reactions involving extremely oxidation labile substrates such as anilines and their derivatives. (C) 2020 Elsevier Ltd. All rights reserved.