Effective metal-free electrooxidative thiocyanation of anilines

An original anodic C–H thiocyanation of anilines with NH₄SCN has been developed, allowing to obtain the products in 88–98% yields under potentiostatic diaphragm electrolysis on glassy carbon electrodes at E_anode = 0.60 V and moderate consumption of electricity. The preliminary voltammetric analysis included the assessment of the changes in the thiocyanate ion curve after the addition of aniline, as well as the measurements of the potentials of the reagents and products, which gave insight into mechanisms of the process (formation of thiocyanate radical and thiocyanogen) and was necessary for its optimization.