Reactions of 1-chloroperfluorocycloalkene derivatives with nucleophiles

Abstract

1-Acetyl- and 1-benzoyl-2-chlorotetrafluorocyclobutene were prepared by the reaction of 2-chlorotetrafluorocyclobutenylcopper reagent with acetyl chloride and benzoyl chloride. 1-Acetyl-2-chloro-, 1-benzoyl 1-benzoyl-2chloro-2-chloro-, and 1-chloro-2-(p-nitrophenyl) hexafluorocyclopentene were prepared by the reaction of 2-chlorohexafluorocyclopentenyl copper reagent with acetyl chloride, benzoyl chloride, and p-iodonitrobenzene, respectively. These compounds contain not only highly activated double bonds but also charge stabilizing groups in vinylic position. These compounds reacted readily with alkoxide, amine, and phosphite to undergo interesting nucleophilic displacement reactions of vinylic chlorine without allylic rearrangement. In reactions of 1-acetyl 1-benzoyl-2-chlorotetrafluorocyclobutene and 1-acetyl- and 1-benzoyl-2-chlorohexafluorocyclopentene with Grignard reagewnt, nucleophilic attack occurred at the carbonyl carbon rather than at the beta-carbon to give tertiary alcohol product.