Fluoroketenes. 10. Synthesis and Chemistry of a Perfluoroacylketene and a Related Perfluorovinyl Ketone

Article abstract of DOI:10.1021/jo00314a032

The synthesis and chemistry of a perfluoroacylketene (12) and a related perfluorovinyl ketone (5) are described.Both are prepared in good yields from a dimer of hexafluoropropene (2).They are thermally stable but very reactive.No acylketene has previously been isolated.Both compounds give the same hydrolysis product and the same product from dimethylformamide.The vinyl ketone, like previously reported perfluoroacryloyl fluorides, is subject to nucleophilic attack at the terminal unsaturated carbon and reacts as a diene in Diels-Alder additions to C=C, C <*> C, C=N, C <*> N, and C=O unsaturation.The acylketene also reacts as a diene togive adducts that are hydrolysis products of the vinyl ketone adducts.