KINETIC SULFUR ISOTOPE EFFECTS IN AROMATIC BROMODESULFONATION
Both bromodeprotonation and bromodesulfonation occur during aqueous bromination of sodium p-methoxybenzenesulfonate, A, and potassium 1-methylnaphthalene-4-sulfonate, B. Whereas for A the bromodeprotonation increases appreciably in amount as the bromide ion concentration is raised, this reaction takes place to a relatively small extent for the less reactive B. A reinvestigation of the kinetics of bromination and a determination of sulfate yields for both of these compounds over a range of bromide ion concentration of 0 to 0.5 M have been made to evaluate the individual rates of these two competing reactions. The kinetic data for the bromodesulfonation of A favor a two-step mechanism with Br2 as the brominating species, but are not considered to eliminate completely a one- or two-step process involving Br+ (or H2OBr+). For B, the kinetics allow either a one- or two-step mechanism with molecular bromine as the brominating agent.Kinetic sulfur isotope effects (k32/k34) have been measured for the bromodesulfonation of A at different bromide ion concentrations. The observed effects are: at [Br−] = 0, 0.3%; at [Br−] = 0.03 M, 1.3%; at [Br−] = 0.5 M, 1.7%. These results confirm the two-step mechanism favored by kinetics and allow the rejection of the alternate mechanism with Br+ (or H2OBr+) as the brominating species. A similar study of B gave the following results: at [Br−] = 0, 0.2%; at [Br−] = 0.25 M, 0.3%; at [Br−] = 0.5 M, 0.4%; at [Br−] = 2.0 M, 0.8%. These results establish the two-step mechanism for this compound and completely eliminate the alternate one-step process.