Reactions of tetrafluoroethene oligomers. Part 15. Reactions of perfluoro-3,4-dimethylhex-3-en-2-one; a highly reactive α,β-unsaturated ketone

Preparation of α,β-unsaturated trifluoromethylketones and their application in the synthesis of heterocycles

“…77 The fluorinated oxirane 189 and azetidine 190 were prepared using the reaction of 186 with NaOCl and primary amines correspondingly.…”

Preparations and reactions of 2-trifluoromethylketenimines

“…Bis(trifluoromethyl)ketenimines have been prepared by perfluoroisobutene or its analogs [5]. More complicated ketenimine has been prepared by the reaction of perfluoro(3,4-dimethylhex-3-en-2-one) with tert-butylamine [6], the reaction of perfluoro(2-methyl-2-pentene) with amines [7], and the reaction of 3,4-dicyano-1,1,1,4,4,4-hexafluoro-2-butene with thiadiazoline [8]. These ketenimines react with nucleophiles to give aldimines [9], heterocyclic compounds [5b, 6,10], and metal complex [11].…”

Reaction of tetrafluoroethene oligomers. Part 17. Some reactions of (E/Z)-perfluoro-2,3-dimethylpenta-1,3-diene

“…Equally, Chambers does not report any evidence for the formation of azetines or oxoazetines and thus it would appear that our reactions, almost certainly by virtue of the presence of the highly reactive ᎐ ᎐ CF 2 group, proceed by a different pathway to those reported. In the light of our recent report of the reactions of perfluoro-3,4-dimethyl-hex-3-en-2-one, 15 where we were able to isolate a ketenimine which cyclised to an azetine, we believe our reactions proceed via a ketenimine of the type X as shown in Scheme 4. We believe X is, as in the methoxide reaction above, formed by a series of addition-elimination reactions.…”