DIRECT LIQUID PHASE FLUORINATION OF HALOGENATED AROMATIC COMPOUNDS

Direct liquid phase fluorination of chlorinated aromatic compounds proceeded by addition and polymerization, yielding the corresponding 1,2,3,4,5,6-hexafluorocyclohexane derivatives, decafluorobicyclohexyls, and low molecular weight polytetrafluorocyclohexenes. The following substrates followed this general reaction sequence: o-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, tetrachlorobiphenyl, and hexachlorobiphenyl. The fluorination of tetrachlorophthatic anhydride yielded 1,2,3,4,5,6-hexafluorotetrachlorocyclohexane-1,2-dicarboxylic acid anhydride. Perfluorobicyclohexyl and low molecular weight polydecafluorocyclohexenes were obtained in the fluorination of hexafluorobenzene; the fluorination of chloropentafluorobenzene proceeded in an analgous manner. The chlorofluorocyclohexanes obtained by the fluorination of o-dichlorobenzene, 1,2,4-trichlorobenzene, and 1,3,5-trichlorobenzene were dehydrohalogenated to give aromatic fluoro and chlorofluoro compounds. Decafluorobiphenyl was obtained in the dehydrohalogenation of decafluorohexachlorobicyclohexyl. Substitution was observed in the fluorination of o-dichlorobenzene. © 1969, American Chemical Society. All rights reserved.