Fluoride ion catalyzed formation of perfluoro esters

Abstract

Trifluoroacetyl fluoride dimerizes at -108°in the presence of CsF to form CF3CO2C2F0. With (CFsfiCFO--Cs+, COF2, CF3C(0)F, C2FóC(0)F, and C3F7C(0)F react to form the heptafluoroisopropyl esters, FCC>2CF(CF3)2, CF3C02CF(CF3)2, 02 0020 (0 3)2, and C3F7C02CF(CF3)2. Although these compounds are formed only at low temperature, when pure they are stable at 25°and above.

Fluorinated [beta]-sultones as Precursors to Fluorinated Sulfonic Acids, and New Fluorosulfonyl Containing Monomers/Polymers

“…data for all fluorinated esters containing the sulfonyl fluoride group are shown in the experimental section, and the spectra are also shown in the appendix.These sulfonyl fluoride esters have several features in common: the stretching frequency for the carbonyl group adjacent to CF2 is found in the 1785-1834 cm-1 region; for the carbonyl group next to the CH 2 group the corresponding frequency is located at 1757 cm-1. These values are in good agreement with other fluorinated esters(19,22,57,58,59). In the silver salt, FS02CF 2 C(O)OAg, the carbonyl frequency is found at 1708 cm-1; while in CF3COOAg, this stretching frequency is located at 1720 cm-1 ( 60) .In all sulfonyl fluoride esters, as well as the silver salt, the asymmetric and symmetric S02 stretching frequencies are assigned to the 1427-1469 cm-1 region and 1209-1259 cm-1 region, respectively.…”

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

“…Its formation by other reactions as a minor or a side product was also reported later [3][4][5][6][7][8][9]. 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 thermal version of the reaction generated only trace amount of SF 5 C(O)F along with other products [30]. The compound (CF 3 ) 2 CFOC(O)F was also prepared earlier [10][11][12]. Compared with 1, these hypofluorites are all of lower thermal stability and decomposition and other reactions were anticipated.…”

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

“…The following thermal elimination step was carried out either in the vapor phase without catalyst, or in the liquid phase with a catalytic amount of alkali fluoride, as described in the literature [9,12] . For example, liquid-phase reaction with 30 mol % of sodium fluoride gave the desired product 1 a in excellent yield.…”