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New catalytic alkylation of in situ generated perfluoro-alkyloxy-anions and perfluoro-carbanions

“…was obtained by reaction of tetrafluoroethylene (TFE) with oxygen in an inert solvent at low temperature using UV irradiation to give a peroxidic perfluoropolyether precursor followed by the reductive cleavage of the peroxide bonds with hydrogen over a suitable catalyst to yield essentially (Z-PFPE) di-acylfluoride products 13 [14][15][16]. The Z-PFPE mono-acylfluoride 12 CF 3 O-(CF 2 CF 2 O) m (C-F 2 O) n -CF 2 C(O)F (Z-MAF) was prepared with good selectivity by direct fluorination of perfluoropolyether diacylfluoride 13 with elemental fluorine in the presence of a catalyst metal fluoride MF (e.g.…”

“…The perfluoroacylfluorides 1 are prepared following standard literature methodology [12][13][14][15][16][17].…”

Synthesis of trifluoromethyl fluoroformate from trifluoromethyl hypofluorite and carbon monoxide: Thermal and catalyzed reaction

“…Another two homologs in this series, CF 3 CF 2 OC(O)F and (CF 3 ) 2 CFOC(O)F, were prepared in low yield through an oxidation of CF 3 CF5 5CFCF 3 in presence of CF 3 OF [10] and a reaction between (CF 3 ) 2 CFO À Cs + and COF 2 [11,12]. These fluoroformates along with others, as a general formula of R f OC(O)F, were probably among the products of the preparation of some PFPE fluids through photochemical oxidation of hexafluoropropene and/or tetrafluoroethylene [3,4,13,14]. However, the products were mixtures of multiple homologs and the preparation of a single fluoroformate through these reactions was unlikely.…”

Peroxidic perfluoropolyether from tetrafluoroethylene oxidation: micro structural analysis by NMR spectroscopy and mechanistic considerations

“…The high rate of oxygen addition to the carbon radicals, close to the diffusion limit, results in the stationary concentration of the carbon radicals being orders of magnitude lower than that of the oxy radicals. Therefore, the radical propagating species are almost exclusively the perfluoroalkylperoxy (RfOO ) and the perfluoroalkoxy (RfO ) radicals [1,2].…”