Organic hypofluorites and their new role in industrial fluorine chemistry

The effect of oxygen in the photocatalytic oxidation pathways of perfluorooctanoic acid

“…As already hypothesized, the perfluorinated oxyradicals preferentially followed a β-scission route by releasing carbonyl difluoride, COF 2 , as a specific by-product, which can be hardly isolated due to its rapid hydrolysis in aqueous media [42]. Carbonyl difluoride is an important intermediate for the industrial synthesis of key fluorinated monomers and it is essential in the preparation of fluoroplastics and perfluororubbers [43][44][45]. In this work, we firstly report that the intermediate COF 2 can be isolated in pure form and in good selectivity by performing the photocatalytic oxidation of PFOA in a suitable perfluorinated aprotic solvent, instead of water.…”

A New Route to Perfluoro(Propyl Vinyl Ether) Monomer: Synthesis of Perfluoro(2-propoxypropionyl) Fluoride from Non-Fluorinated Compounds

“…PPVE could be made either by dechlorination of perfluorinated dichloroether 2 (Route I) [4,5] or by thermal elimination of perfluorocarboxylic acid derivatives 1 a±c (Route II) [3] . Compound 2 could be obtained by direct fluorination of the corresponding hydrocarbon dichloroether 3.…”

“…[1,2] However, it has disadvantages in that it is expensive because so far, it has been prepared from hexafluoropropylene oxide (HFPO), which is itself very costly (Scheme 1). [3] Recently, use of perfluorinated hypofluorite chemistry [4] was reported to lead to an improved process. Also, the synthesis of perfluoro(alkyl vinyl ethers) by direct fluorination of partially fluorinated 1,2-dichloroethyl ethers has been reported.…”

An Environmentally Friendly Class of Fluoropolyether: α,ω-Dialkoxyfluoropolyethers

“…The stability of these species depends on the nature of metal fluoride [16], temperature, and the solvent [17]. Metal perfluoroalkoxides are also important industrial intermediates in the synthesis of hypofluorites like CF 3 CF 2 OF [18] and fluorinated vinylethers [19,20]. Completely anhydrous reaction conditions are required, because in presence of water the hydrolysis of acyl fluoride groups generates hydrofluoric acid, HF, which can be absorbed by the solid metal fluoride giving MHF 2 [16].…”