Tadashi Okuyama, Masayoshi Toyoda, Takayuki Fueno
1990
Citations
0
Influential Citations
8
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Methoxymethyl phenyl sulfoxide 1 undergoes acid-catalyzed hydrolysis to give S-phenyl benzenethiosulfinate 5, which is formed rapidly from a primary product, benzenesulfenic acid 3. Formation of 5 follows pseudo-first-order kinetics. Rate constants obtained spectrophotometrically in perchloric acid show that the reaction is dependent on the protonated substrate with the Bunnett–Olsen φ=−0.15. Rate constants for the loss of optical activity of the enantiomeric 1 measured in 80 vol% aqueous dioxane are identical with those obtained spectrophotometrically for the formation of 5. Racemization of the substrate does not take place more rapidly than the fragmentation. The reaction is accelerated by chloride and bromide ions. The halide reaction is first order in acid concentration.