Radical additions to fluoroolefins. Thermal reaction of perfluoroallyl chloride with perfluoroalkyl iodides as a selective synthesis of terminal perfluoroolefins

Reaction ofperiluoroallyl chloride w>ith perfluoronlkyl iodldez, R, I ( R,- =C,F,, C,F, 1. C,F,,), in an autoclave at 180-250 “C gave terminal perfluoronlefins. CF?=CF-CF:-R, ( 24) ah the xole reaction products. lsomeric fluoroolefins containing an internal double bond and telomeric products were not observed m the reaction mixture. The yields were dependent on the reaction temperature and on the chain length of R& the highest preparative yield of olcfin 2 (K,. =C,F,) was obtained at 200 “C (26%). while in the syntheses of olefins 3 and 4 (R,=C,F,landC,F,,. respectively ) highest yields were achieved at 750 “C ( 41 ?J- and 747~, respectively). The presence of CuI or a peroxide initiator had a negative influence on the yield of products. Formulae have been awgned to the fragments in the mass spectra of products