Acid-catalyzed decomposition of diazodiphenylmethane in dimethylsulfoxide

Acid-catalyzed decomposition of diazodiphenylmethane (DDM) has been studied in DMSO containing varying amounts of water. The reaction was found to be first-order in DDM and first-order in acid. The Bronsted plot for a series of carboxylic acids is curved with the H+ point falling below the curve defined by the carboxylic acids. In near-anhydrous DMSO, kinetic hydrogen isotope effects (KIEs) are 1.7 and 1.6 for acetic acid and chloroacetic acid, respectively. The chloroacetic acid KIE increases with increasing water concentration, rising to 2.9 at 3.6 M water. As a function of [H2O], k(HA) for chloroacetic acid shows a sharply defined minimum occurring at 1 M water. This behavior and the water effect on KIE suggest that the carboxylic acid-catalyzed reactions in near-anhydrous DMSO do not use the AS(E)-2 mechanism attributed to the reaction of DDM in hydroxylic solvents. A mechanism, leading to an azoalkane, is suggested. Either directly or indirectly, this may lead to diphenylcarbene, which would account for the observed products: benzophenone, benzhydrol, and benzhydryl esters. For the H+ catalyzed decomposition of DDM in near-anhydrous DMSO, benzophenone is not found among the products, and we suggest that this reaction does not undergo a change in mechanism and continues to use the AS(E)-2 mechanism.