SYNTHESIS OF PERFLUOROBICYCLIC ETHERS . THE ELECTROCHEMICAL FLUORINATION OF α-CYCLOHEXENYL-SUBSTITUTED CARBOXYLIC ACID DERIVATIVES

Article abstract of DOI:10.1016/S0022-1139(00)81474-8

The electrochemical fluorination of α-cyclohexenyl-substituted carboxylic esters < formula (R=H, CH3, C2H5, C3H7; R'=CH3, C2H5, C3H7)> afforded both perfluoro (9-alkyl-7-oxa-bicyclo<4.3.0>nonane)s and perfluoro(8-alkoxy-9-alkyl-7-oxabicyclo<4.3.0>nonane)s in fairly good yields.As the driving force for the ring-closure in this fluorination, a mechanism which involves a resonance stabilized intermediate radical is proposed. Perfluoro(8-chloro-8-methoxy-9-ethyl-7-oxabicyclo<4.3.0>nonane) and perfluoro(8,8-dichloro-9-ethyl-7-oxabicyclo<4.3.0>nonane) were obtained by the controlled chlorination of perfluoro(8-methoxy-9-ethyl-7-oxabicyclo <4.3.0>nonane) with anhydrous aluminum chloride in low yields.Some new fused perfluorobicyclic ethers and a perfluoroacid fluoride obtained in this experiment have been characterized by infrared, mass and 19F nmr spectra and elemental analysis.