Chemistry of Haloperfluoro Compounds. Reactions of Metal F-Alkoxides and Metal F-Acetates with F-2-Butyne.

摘要

Methods were developed for the preparation of a variety of new carbon-oxygen-fluorine containing compounds utilizing as starting reagents metal F-alkoxides,derived from the corresponding carbonyl compound and metal fluorides,or F-acetates,and F-2-butyne. (E)-2-Bromo-3-(F-alkoxy)-F-2-butenes were prepared by the addition of silver F-alkoxides to F-2-butyne in the presence of the bromine transfer reagent 1,2-dibromotetrachlorethane. F-1,2,4,4,6,6-Hexamethyl-3, 5-dioxacyclohexene,IX,and F-3,4-dimethyl-3-penten-2-one, X,were formed by the reaction of (E)-F-1-methyl-propenylsilver with F-propanone and by the reaction of F-propanone with F-2-butyne in the presence of cesium fluoride. Compound X was also prepared from F-propanone and F-2-butyne in the presence of silver F-acetate. Compound X readily underwent photochemical cyclization to give F-1,2,4,4-tetramethyl-3-oxacyclobutene,XI. The thermal reactions of IX and XI and the reactions of IX, X and XI with cesium fluoride were investigated. The order of thermodynamic stability was IX>X>XI. Reaction of silver F-acetate with F-2-butyne in the presence of 1,2-di-bromotetrachloroethane gave (E,Z)-2-bromo-3-(F-acetoxy)-F-2-butene,XIII. (Author)