David C. England

Fluoroketenes VII. Synthesis and reactivity of trifluoromethylfluoroketene, perfluoroacryloyl fluoride, perfluoromethacryloyl fluoride, methyl perfluoroacrylate and methyl perfluoromethacrylate

Abstract Trifluoromethylketene has been detected by trapping reactions, but has not been isolated. In the absence of a trapping agent, reactions designed to give the ketene gave its isomer, perfluoroacryloyl fluoride. Convenient syntheses are described for saturated precursors to perfluoroacryloyl fluoride, methyl perfluoroacrylate and methyl perfluoromethacrylate, and conditions are given for the dehydrofluorination of these precursors to the acrylates. Some chemistry of perfluoromethacryloyl fluoride [available from bis(trifluoromethyl)ketene through equilibration], perfluoroacryloyl fluoride and the related methyl esters are reported, particularly Michael additions, 1,2 cyclo-additions and free-radical reactions.

Reactions of amines with a dimer of hexafluoropropene and with a perfluorovinyl sulfide prepared with hexafluoropropene

Abstract Some reactions of amines with a perfluorovinylsulfide, (CF 3 ) 2 CFSC(CF 3 )CFCF(CF 3 ) 2 , prepared from hexafluoropropene (HFP) and sulfur [1] are compared to reactions of the same amines with the thermodynamic dimer of HFP, (CF 3 ) 2 CCFCF 2 CF 3 . Many new ketenimines, eneamines, amidines, nitriles, and quinoline derivatives are reported.

Fluoroketenes VIII. Adducts of perfluoromethacryloyl fluoride with unsaturated molecules. N-alkyl-bis(trifluoromethyl)ketenimines☆

Abstract Perfluoromethacryloyl fluoride has been found to yield predominantly 1,4 cyclo-adducts with olefins, isocyanates, nitriles and ketenes. With olefins and isocyanates, 1,2 cyclo-adducts and open-chain adducts are also formed, and evidence is presented to indicate that such adducts are obtained via dipolar intermediates. A new synthesis of N -alkyl-bis(trifluoromethyl)ketenimines is also reported.

Fluorovinylketones from perfluoropentene-2

Abstract Two fluorovinylketones have been prepared from methoxy- perfluoropentenes using a new reaction involving catalytic loss of methyl fluoride. One of these vinylketones reacted as a diene with propenyl propyl ether.

Fluoromonomers and other compounds from fluoroolefins

Abstract Three basic fluoroolefins, tetrafluoroethylene, hexafluoropropene and octafluoroisobutene are available from difluorocarbene (pyrolysis of chlorodifluoromethane). They have been used to prepare a wide variety of materials with unusual properties and chemistry. These include polymerizable monomers and other compounds containing various functional groups. Discussion will include the chemistry of some epoxides, perfluoro-2-methylene-4-methyl-l,3-dioxolane, perfluoroacrylonitrile, 2,3,3-trifluorocyclobutene-l-carbonitrile, perfluoroallyl fluorosulfate, fluorosultones and fluorosulfides.