Sylvie Benefice-Malouet

Reactivite comparee des perfluoroiodoalcanes (RFI) et des perfluoroalcoyl-2 iodo-1 ethanes (RFC2H4I) en presence de couple metallique zinc-cuivre dans les solvants phosphates d'alcoyles

Abstract Reactivity of perfluoroalkyl iodides R F I and 1-perfluoroalkyl-2-iodoethanes R F C 2 H 4 I, in presence of a zinc-copper couple in alkyl phosphates solvents, is described. R F I and R F C 2 H 4 I react via an organometalllc route to give per- and poly-fluoroorganozinc (R F ZnI and R F C 2 H 4 ZnI) compounds. Then, in particular conditions, they react with alkyl to give phosphoro-fluorinated molecules (phosphinates, phosphine oxides, phosphines). The compoundss stabilities are studied.

Mise au point d'un procede de preparation catalytique de perfluoroalkyl sulfonamide par addition d'ethylamine a un chlorure d'acide perfluoroalcane sulfonique

Abstract Addition of N-ethylamine to a perfluoroalkylsulfonic acid chloride R F SO 2 Cl has been studied, to obtain the corresponding perfluoroalkylsulfonamide R F SO 2 NHC 2 H 5 . First a two-step synthesis has been considered : transformation of the perfluoroalkylsulfonic acid chloride R F SO 2 Cl to the corresponding fluoride R F SO 2 F, and addition of N-ethylamine; the study of the first step is reported. Then, a sulfonamide one-step synthesis involving a fluoride catalysis, is described.

Synthese d'acides perfluoroalcane carboxylique et sulfinique par reduction electrochimique d'iodures de perfluoroalkyle sur cathode en fibres de carbone dans le solvant N,N dimethylformamide. Application a la synthese de perfluoro α,ω diacides.

Abstract The electrochemical reduction of C 6 F 13 I on a carbon fibre cathode in DMF as solvent and in the presence of SO 2 is studied. Depending on the water content of the solvent, perfluorohexyl sulfinic acid C 6 F 13 SO 2 H or perfluoropentyl carboxylic acid C 5 F 11 COOH are obtained. These reactions are applied to 1,4-diiodoperfluorobutane; by varying the composition of the solvent it has been possible to obtain the two diacidic compounds: HO 2 S(CF 2 ) 4 SO 2 H and HO 2 S(CF 2 ) 3 COOH.

Synthese de perfluoro-nhexyl-2 ethanol C6F13C2H4 OH par reduction electrochimique sur fibres de carbone de perfluoro-nhexyl-2 iodo-1 ethane C6F13C2H4I dans le solvant N,N dimethylformamide.

Abstract Electrochemical reduction of 2-perfluoro-nhexyl-1-iodo-ethane at a carbon fibre cathode, in N,N-dimethylformamide as solvent, leads to the perfluoro-nhexyl-2-ethanol with perfluoro-nhexyl-2-ethylene as the major by-product. A mechanism is proposed on the basis of results obtained from macro-scale electrolysis and a study of Linear Sweep Voltammetry.

Reactivity of the electrogenerated superoxide anion with F-alkyl halides (I, Br) andα,ωF-alkyl diiodides

Abstract The electrogenerated superoxide ion O − 2 · reacts with F-alkyl iodides and bromides and with α-ω F-alkyl diiodides, affording perfluoroalkyl carboxylic acids and diacids. Linear sweep voltametric investigation of the mechanism lead us to obtain an estimation of the kinetic parameter involved in the first step: Further evolution of the radical R F O 2 · is interpretated as proceeding via two routes: All the species involved are stoichiometrically converted finally into F-alkyl carboxylic acids: When working with diiodo compounds I(CF 2 ) 4 I, mono and dicarboxylic acids are obtained selectivity at a preparative scale, a result which is interpreted through a voltametric analysis of the mechanism.