T. Okuyama, T. Fueno
Oct 1, 1992
Citations
0
Influential Citations
2
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Hydrolysis of methoxymethyl benzenesulfenate is catalyzed by both acid and base. Acid-catalyzed hydrolysis is further accelerated by various nucleophiles like halide ions, thiocyanate, dialkyl sulfide, and the substrate itself. The catalytic constants coincide with those for ethyl benzenesulfenate within 2-fold in magnitude. The nucleophilic reactivity strongly suggests the reaction at the sulfenyl sulfur, but examination of the products from the 18O-labeled substrate showed that the bond cleavage occurs mostly between the oxygen and the proformyl carbon except for the acid-catalyzed water reaction which undergoes the S–O cleavage. A mechanism for a nucleophilic reaction at the sulfur to form a sulfurane intermediate which breaks down with the C–O cleavage is presented. The hydrolysis rate is also strongly dependent on the second order of buffer concentrations in carboxylate and tertiary amine buffer solutions. The third-order term involves both the general acid and the conjugate base of the buffer, and t...