Abstract
Oxygenation of toluene was investigated with bis(3-nitrobenzenesulfonyl) peroxide (NBSP) in the presence of salts known to affect radical (cupric, cuprous, and cobaltous chlorides, and sodium hexachloroiridate (IV)) and ionic (aluminium chloride) processes. The yield and orientation of the isomeric tolyl 3-nitrobenzenesulfonates, as well as a kinetic study, show that salts which bring about radical pathways do not catalyze oxygenation, although induced decomposition of peroxide is accomplished with formation of sulfonate salts. Aluminium chloride has a promoting effect on aromatic oxygenation at AlCl 3:NBSP ≅ 4:1, but at lower ratios rapid breakdown of the sulfonyl peroxide is effected in a competing reaction. The results are interpreted in terms of nucleophilic displacement by the aromatic nucleus at the peroxidic oxygen-oxygen bond in accord with the earlier proposal of Dannley and analogous to attack of stronger nucleophiles on aroyl peroxides.
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