HYDROXYALKANESULFONYL CHLORIDES FROM CHLORINATION OF HYDROXYALKANESULFINATE SALTS IN A NONPOLAR MEDIUM: 3-HYDROXY-1-PROPANESULFONYL AND 4-HYDROXY-1-BUTANESULFONYL CHLORIDES

Abstract

3-Hydroxy-1-propanesulfonyl chloride (1b) was obtained for the first time (admixed with 10% of propane sultone, 2b) by chlorination of a dichloromethane suspension of sodium 3-hydroxy-1-propanesulfinate (3b). 4-Hydroxy-1-butanesulfonyl chloride (1c) containing 13% butane sultone (2c) was prepared similarly from 3c. The cyclizations of 1b and 1c in CDCl₃ containing 1-butanol (0.9 M) showed first order rate constants of 1.4 × 10^?4 and 6.4 × 10^?5 s^?1, corresponding to effective concentrations of 4.5 × 10² and 2.1 × 10² M, respectively. Reaction of triethylamine in ethanol-d (a) with 1b gave exclusively the undeuterated sultone (2b), evidently by a direct cyclization, and (b) with 1c produced mainly ethyl 4-hydroxy-1-butanesulfonate largely monodeuterated at the α-position, and presumably formed by way of the sulfene (6c).