New bifunctional compounds derived from perfluoroolefins

Electrocatalytic Oxidation of Perfluoroalkylvinyl Ethers in Fluorosulfonic Acid

“…These results differ from [3] in that the dimer product contains a single isomer formed by dimerization of the radicals (6) "headto-head." The HFP transformation occurs as follows:…”

“…Until this paper, the only example of galvanostatic fluorosulfation of terminal fluoroolefins, described in the literature, was the electrolysis of hexafluoropropylene (HFP). The dominant products of this reaction are isomeric "head-to-head" or "head-to-tail" fluorosulfatodimers at a molar ratio of 2 : 1 [2,3]. Under conditions of galvanostatic electrolysis in HSO 3 F, the dominant electrochemical process is the anodic oxidation of fluorosulfonyloxy anion, which yields PDF, whose interaction with fluoroolefin has a well-pronounced radical nature.…”

Electrochemical fluorosulfation of perfluoroalkyl vinyl ethers

“…An alternative pathway of the forma tion of these compounds by recombination of the primary radicals FSO 2 OC(R)FCF 2 • (R = CF 3 or OR F ), which are generated through the addition of the FSO 3 • radical at the C β atom of the double bond, with the correspond ing secondary radicals 12 should be rejected because tail to tail fluorosulfate dimers were never detected in any of these two processes.…”

“…This peroxide is rather stable and, at the same time, readily dissociates into radicals (the energy of O-O bond homolysis is ∼37 kcal mol -1 ). The reaction products are formed mostly due to addition of the FSO 3 • radical to fluoroolefin. This can be illustrated by electrochemical fluorosulfation of tetrafluoroethylene 1 (Scheme 1).…”