| The generality of sulfide amination with O-mestylenesulfonylhydroxylamine was demonstrated with the synthesis of fourteen new sulfilimine salts. The exploratory reaction of sulfide with hydroxylamine-O-sulfonic acid appeared to work best in aqueous solution.;These data were analyzed using two and three dimensional reaction surface where the axis of these surfaces were N-H bond making (Bronsted (alpha)), S-S bond making ((beta)(,nuc)) and S-N bond breaking ((beta)(,lg)). The results are consistent with a completely concerted, 'SN(,2)' transition state with rate limiting proton transfer.;Rate constants for the thiolate reduction of S-methyl-S-(substituted)phenyl sulfilimine salts in aqueous, weak acid media was measured. General-acid catalysis were observed. Analysis of the rate constants yield Bronsted (alpha) equal ('(TURN))0.5 for reduction with 3-nitro-5-thiobenzoic acid, NTBA, and ('(TURN))0.9 for reduction with 3-thiobenzoic acid, M-TBA. Solvent deutrium isotope effect was measured, k(,H)/k(,D) values were large, ('(TURN))7 for NTBA and ('(TURN))2 for m-TBA reductions. Hammett plots using the second order rate constant, k(,H), against (sigma)('n) were not linear. Values of (beta)(,nuc) were measured using k(,h) and k(,HB) in acetic acid as the rate constants. The (beta)(,nuc) against (sigma)('n) showed a large dependence of the pKa of the catalyzing acid. |
