Kinetic and mechanistic investigation of the ozonolysis of 2,4-xylidine (2,4-dimethyl-aniline) in acidic aqueous solution

The ozonolysis of 2,4-xylidine (2,4-dimethyl-aniline) in acidic aqueous solution was investigated by determining the major reaction products and their evolution as a function of the reaction time and their dependence on the pH of the reaction system. 2,4-Dimethyl-nitrobenzene and 2,4-dimethyl-phenol were found to be primary reaction products; their formation might be explained by electron transfer and substitution reactions. 2,4-Dimethyl-phenol was further oxidized yielding 2,4-dimethyl- and/or 4,6-dimethyl-resorcinol by electrophilic addition of HO(center dot) radicals. The best fitting phenomenological kinetic model and the good convergence of calculated and experimentally determined rate constants imply two additional competitive pathways of substrate oxidation: (i) electrophilic addition of HO(center dot) radicals and fast subsequent substitution would also yield the resorcinol derivatives. (ii) Substrate and isolated products are thought to be oxidized by hydrogen abstraction at the benzylic sites, but the corresponding products (alcohols, aldehydes, and carboxylic acids) could not be identified. Fe(II) was added to probe for the presence of H(2)O(2), but had no or only a minor effect on the kinetics of the ozonolysis. (c) 2009 Elsevier B.V. All rights reserved.