Substitution sulfonyl peroxides

Electron-donating substituents make the aromatic subsU ate more reactive than benzene and lead to o,/ -orientation, while electron-withdrawing substituents decrease the reactivity and give mostly m-orientation products. The detailed mechanism of the formation of the a complex has been studied by oxygen-18 labeling of the sulfonyl oxygen in p-nitrobenzenesulfonyl peroxide. The ionic mechanism for aromatic substitution by sulfonyl peroxides has been confirmed by carrying out the substitution reaction in the presence of redox catalysts such as copper and cobalt salts and aluminum chloride. Small differences in the rate of the products can be found in the presence or absence of these additives, and it has been concluded that the ionic mechanism accounts satisfactorily for these results. ... 

Perfluorophenylsulfonyl chloride and its 4-substituted derivatives 5 are prepared from reaction of the thiols 4 with chlorine in acetic containing the amount of water calculated for formation of the sulfonyl group.287 The initially formed precipitate of disulfide is slowly dissolved, Surprisingly, in the case of the 4-acetamido derivative, the oxidation is accompanied with desulfuration. The use of hydrogen peroxide does not have a substantial influence on the desulfuration process.287... 

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