TERT-BUTYL CATION FORMATION IN THE HYDROLYSIS OF 2-METHYL-2-PROPANESULFONYL CHLORIDE, THE SIMPLEST TERTIARY ALKANESULFONYL CHLORIDE

Evidence is presented that the only significant reaction of 2-methyl-2 -propanesulfonyl chloride (1) (a) in water over the pH range 3.5-13.0 or (b) in methanol-chloroform-d is an ionization to the tert-butyl cat ion (2) and the chlorosulfite anion (ClSO2-), followed by further reac tions of these species. The organic products include isobutylene (3), tert-butyl chloride (4a), tert-butyl alcohol (4b), and, at high pH, 2- methyl-2-propanesulfinate anion (6) and small amounts of 2-methyl-2-pr opanesulfonate anion (5). In the presence of barium chloride the rate of hydrolysis of 1 is constant over the pH range 3.5-12.0.