Halomethyl-Metal Compounds, LXXVII. An Organomercury Route to Tetrafluoro-Ethylidene.

摘要

Phenyl(1-bromo-1,2,2,2-tetrafluoroethyl) mercury has been prepared by reaction of phenylmercuric chloride and 1-bromo-1,2,2,2-tetrafluoroethane with sodium methoxide in THF at -35 C. This mercurial readily transferred CF3CF to carbenophiles at 155 C. With olefins good yields of gem-fluoro(trifluoromethyl) cyclopropanes were obtained and with triethylsilane Si-H insertion gave Et3SiCHFCF3. On reaction with thiobenzophenone, the intermediate thiirane underwent loss of sulfur to give Ph2C=CFCF3. A similar observation was made in the reactions of PhHHgCFBrCO2Et with thiobenzophenone and thiofluorenone. Phenyl(1-bromo-1,2,2-trifluoro-2-ethoxyethyl) mercury also was prepared, but this compound did not exhibit divalent carbon transfer reactivity. (Author)