Synthesis of new phosphonic derivatives bearing fluorinated chains

We describe various radical telomerization reactions of chlorotrifluoroethylene (CTFE) and dialkyl hydrogenphosphonates (HP(O)(OR)2 R=Me, Et). Characterization by 1H, 19F and 31P NMR of the resulting telomers are detailed. For the heaviest telomers, we used MALDI-TOF analyses to give the mass values. Parameters such as pressure, solvent, R0, C0, temperature and nature of initiator have been studied in order to optimize this reaction. Some products have been prepared in large quantities using special high-pressure reactors. We also succeeded in the cleavage of phosphonic esters in order to obtain acidic structures well-known for their adhesive properties on metals.