Electrochemical synthesis of two N,N,N',N'-tetraalkyl-4,4'-azodianiline derivatives was carried out via electrochemical oxidation of N,N-dialkyl-p-phenylenediamine in an aqueous solution. The results showed that electrochemically generated p-quinone-diimines in a Michael-type reaction with the starting molecules (N,N-dialkyl-p-phenylenediamine) and via an "electron transfer + dimerization reaction + electron transfer" (ECE) mechanism, were converted to the corresponding N,N,N',N'-tetraalkyl-4,4'-azodianiline derivatives. In this work, two tetraalkyl-4,4'-azodianiline derivatives with high yields in aqueous solutions, without toxic reagents and solvents at a carbon anode electrode using an environmentally friendly novel method, are provided. (C) 2014 Elsevier E.V. All rights reserved.