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Abstract The electronic effects on the mechanism of the Baeyer— Villiger reaction were examined. A series o p,p’disubstituted. benzophenones were prepared and oxidized, using 40% peracetic acid in methylene chloride and tnfluoroacetic acid as catalyst. from the relative migratory aptitudes of p-substituted phenyl groups, it was established that a free radical mechanism predominates. Another set of p,p’-disubstltuted benzophenones were oxidized by trifluoroperacetic acid in methylene chloride. In this case the relative migratory aptitudes of different substituents were similar to their reactivity toward electrophilic substitution. Thus it was concluded, as was established by many investigators, that a cationic mechanism predominates here. In general, it was observed that a free radical mechanism predominates if the leaving group was acetyl, and that a cationlo mechanism predominates if the leaving group was tn— fluoroacetyl, which is more strongly electron attracting. |