Free Radical Hydrophosphorylation of Fluoroalkyl Vinyl Ethers: Synthesis of Fluoroalkyl Phosphonates

An effective method for the synthesis of dialkyl [2-(polyfluoroalkoxy)ethyl]phosphonates by free radical hydrophosphorylation of fluoroalkyl vinyl ethers with dialkyl (H)-phosphonates was developed. The reaction proceeds in the presence of catalytic amounts of azabisisobutyric acid dinitrile (AIBN) (150°C, 2 h, portionwise addition of AIBN) to afford the target fluoroalkyl phosphonates in up to 85% isolated yield.