Electrochemically induced reactions of some fluorocarbon derivatives

Abstract

The oxidation of polyfluoroanisoles gave the corresponding 4,4.''-dimethoxybiphenyl derivatives. A vacant para position was shown to be a necessary condition for this coupling reaction. The electron transfer process was found to be thermodynamically irreversible by cyclic voltammetry. Oxidation of polyfluorinated aromatic amines and phenols generally gave multi-component mixtures, although their voltammetry was simple. The oxidation of pentafluorophenol was greatly Improved by the use of trifluoroacetic acid as solvent. The reaction of octafluorobut-2-ene with some amines was Investigated, Products from reaction with primary amines adopted the imine form; the lack of reaction with diethylamine was accounted for by steric hindrance, Trans-2H-heptafluoro- but-2-ene behaved similarly. The Influence of solvent on the reaction between hexafluorobut-2-yne and diethylamine was Investigated, Oxidation of fluorinated amino-alkenes gave dimeric products if there was an unsubstituted position at the double bond. Reduction of perfluorocyclohexene gave oligomers. Reduction of perfluorocyclopentene in N,N-dimethylformamide gave a polymer; no reduction In acetonitrile was noted. Only trapping with perfluorocyclohexene was successful, no polymer was produced and cooligomers were produced. Reduction of 2,3-dlchloro-hexafluorobut-2-ene gave poly(hexafluorobut-2-yne). Hexafluorobut-2-yne could not be reduced electrochemically.