Homolytic reactions of perfluoroaromatic compounds. Part III. Reactions of benzoyl peroxide with hexafluorobenzene, chloro-, bromo-, and nitro-pentafluorobenzene, and pentafluoropyridine

Abstract

The reaction of benzoyl peroxide with hexafluorobenzene has been shown to give 2,3,4,5,6-pentafluorobiphenyl and a residue whose relative yields depend mainly on the conditions used for the distillation of the biaryl from the reaction mixtures. This supports the suggestion made previously that the biaryl is formed partly by defluorination of σ-complexes during reaction, and partly by thermal breakdown of dimers of the σ-complexes during the distillation. Analogous phenylation of chloro-, bromo-, and nitro-pentafluorobenzene and pentafluoropyridine gives mixtures of isomeric products. The ratios in which these isomers are formed with chloro- and bromo-pentafluorobenzene and pentafluoropyridine have been measured and are discussed.