The reactions of electrochemically generated o-quinones, as Michael acceptors, from oxidation of catechols with trialkylphosphites as nucleophiles have been studied using cyclic voltammetry. The reaction mechanism is an EC mechanism and the products of reaction are believed to be dialkylphosphonate derivatives of catechol. The observed homogeneous rate constants (k(obs)) for reactions were estimated by comparing the experimental voltammetric responses with the digitally simulated results based on the proposed mechanism. A quantitative relation between half-wave potentials of catechols and the reactivities of their corresponding o-quinone were derived. Also the effects of substituted group of trialkylphosphites on rate constants of chemical reactions were studied. (C) 2012 Elsevier Ltd. All rights reserved.