[<i>p</i>-((Trifluorovinyl)oxy)phenyl]lithium: Formation, Synthetic Utility, and Theoretical Support for a Versatile New Reagent in Fluoropolymer Chemistry

Abstract

The metal−halogen exchange reaction of p-bromophenyl trifluorovinyl ether, p-BrC6H4OCFCF2 (1), with tert-butyllithium in ether at −78 °C affords the title reagent, p-LiC6H4OCFCF2 (2), in solution. Subsequent addition of appropriate silicon, phosphorus, or organic electrophiles yields a wide variety of new trifluorovinyl ether monomers for fluoropolymer chemistry. Ab initio calculations (MP2/6-31G*//6-31G* level) indicate that the (trifluorovinyl)oxy substituent stabilizes anion 2 by approximately 10 kcal/mol relative to the methoxy analogue.