Fluoro-ketones. II Reactions of fluorocarbon grignards and copper compounds with perfluoroalkylacid fluorides

Abstract

The reactions between C 6F 5MgBr (I), p-BrC 6F 4MgBr (X), C 6F 5Cu (XXI), p-HC 6F 4Cu (XXII) and p-BrC 6F 4Cu (XV) with primary and secondary perfluoroalkylether acid fluorides were studied. The Grignard compounds react very slowly with the secondary acid halides (R fCF(CF 3C(O)F) whereby competing reactions cause undesirable by-products and reduction of ketone yields. Primary acid halides (R fCF 2C(O)F) react much faster with C 6F 5MgBr to give the ketone in improved yields. The organocopper compound react with either primary or secondary acid halides to give the ketone in excellent yields with no by-product formation from competing secondary reactions. Solvent, type of organometallic reagent and primary versus secondary acid fluoride are variables that influence product yield and product distribution.