[<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 -BrC 6 H 4 OCF CF 2 ( 1 ), with tert -butyllithium in ether at −78 °C affords the title reagent, p -LiC 6 H 4 OCF CF 2 ( 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.