Perfluoroalkanesulfonyl Chlorides Research Articles

A General Method for the Preparation of Perfluoroalkanesulfonyl Chlorides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A general method for the preparation of perfluoroalkanesulfonyl chlorides

A mild two-step synthesis of perfluoroalkanesulfonyl chlorides starting from perfluoroalkyl iodides has been developed. Reaction of perfluoroalkyl iodides with sodium dithionite gave sodium perfluoroalkanesulfinate salts which were converted into perfluoroalkanesulfonyl chlorides in 25–73% yield (two steps) using N-chlorosuccinimide.

ChemInform Abstract: Direct Perfluoroalkylation of Aromatic and Heteroaromatic Compounds with Perfluoroalkanesulfonyl Chlorides Catalyzed by a Ruthenium(II) Phosphine Complex.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Direct perfluoroalkylation of aromatic and heteroaromatic compounds with perfluoroalkanesulfonyl chlorides catalysed by a ruthenium(II) phosphine complex

The perfluoroalkylation of aromatic and heteroaromatic compounds by perfluoroalkanesulfonyl chlorides 1 has been investigated in the presence of a ruthenium(II) phosphine complex. The reaction of compounds 1 with substituted benzenes or thiophenes proceeded smoothly with extrusion of sulfur dioxide at 120 °C to give corresponding perfluoroalkylated compounds in good yield. No expected perfluoroalkylated product was obtained in the reaction of compounds 1 with pyrrole; however, 1-trimethylsilyl- and 1-triisopropylsilyl-pyrrole were regioselectively perfluoroalkylated at their 2- and 3-position, respectively.

Electrochemical synthesis of perfluoroalkanesulfinic acid derivatives

It has been shown that perfluoroalkyl iodides react with thiolate anions under electrochemical initiation [N.V. Ignat'ev, S.D. Datsenko and L.M. Yagupolskii, Zh. Org. Khim. 27, No. 5, (1991) 905]. However, the reactivity of S- nucleophiles with sulfur atoms in a high oxidation state is much lower. We have studied the reaction of perfluoroalkyl halides with methyl sulphites. These compounds are easily prepared by bubbling of SO 2 through a sodium or lithium methylate solution: SO 2+NaOCH 3→CH 3OSO 2Na R FX CH 3OSO 2 −+2e −→ R FSO 2 −+CH 3O −+X − RCF 3, C 3F 7, C 8F 17; XI, Br The reaction of the anion −SO 2OCH 3 formed with the perfluoroalkyl halides under the electrochemical reduction conditions leads to the perfluoroalkane sulfinates in a high yield (95%). Though methyl sulphites contain two nucleophilic centres, sulfur and oxygen, the perfluoroalkyl radical attacks exclusively on the sulfur atom. This seems to be connected with the ‘hard’ oxygen centre. The treatment of the reaction mixture resulting from the electrochemical synthesis with chlorine leads to the formation of the corresponding perfluoroalkane sulfonyl chlorides, useful starting materials for the production of organofluorine compounds, in high yield: R FSO 2 −+Cl 2→R FSO 2Cl

ChemInform Abstract: Novel Perfluoroalkylation of Alkenes with Perfluoroalkanesulfonyl Chlorides Catalysed by a Ruthenium(II) Complex.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reactions of Perfluoroalkanesulfonyl Chlorides with Aromatic Compounds Catalyzed by a Ruthenium(II) Complex.

AbstractThe aromatic compounds (I) react with the perfluoroalkanesulfonyl chlorides (II) to form the substitution products (III).

Reactions of Perfluoroalkanesulfonyl Chlorides with Aromatic Compounds Catalyzed by a Ruthenium(II) Complex

Abstract The reactions of perfluoroalkanesulfonyl chlorides with aromatic compounds in the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II) were found to give perfluoroalkylated compounds in good yield.

The reactions of perfluoroalkanesulfonyl bromide with hetero-atom substituted olefinic bonds

Perfluoroalkanesulfonyl bromides reacted with vinyl bromide, vinyl acetate and trimethyl vinyl silane to give the corresponding adducts with the evolution of SO2. Perfluoroalkanesulfonyl bromide reacted with trimethyl silyl enol ether followed by hydrolysis to give the corresponding α-bromoketones and perfluoroalkanesulfinic acid. However, perfluoroalkanesulfonyl chlorides reacted with trimethyl silyl enol ether of pinacolone on UV irradiation to give the corresponding α-perfluoroalkyl derivatives of pinacolone. Under mild condition, perfluoroalkanesulfonyl bromide also brominated phenol and anisole to give the corresponding p-bromo derivatives. Sodium α, α-dichlorotrifluoroethanesulfinate reacted with bromine in water at 25°C to form α, α-dichlorotrifluoroethanesulfonyl bromide which was thermally less stable than but similar in reactivity to perfluoroalkanesulfonyl bromide.

Thermolyse des halogenures de perfluoroalcanesulfonyle

Perfluoroalkanesulfonyl chlorides [R FSO 2Cl ; R F  CF 3, C 2F 3, C 4F 9], decompose thermally to give the corresponding perfluoroalkyl chlorides with evolution of SO 2. The latter retards the reaction, but it is catalysed by copper which also inhibits the SO 2 effect. 2-methyl-2-nitrosopropane traps the perfluoroalkyl free radicals. In the presence of a perfluoroalkyl iodide [R′ FI ≠ R′ F≠R F], other products, R FI and R FCl, are obtained. A free radical chain-mechanism is then suggested. On the other hand, perfluorobutanesulfonyl fluoride is very stable thermally.

The syntheses of fluorinated alkanesulfonamides and poly-(fluorinated alkanesulfonamides)

In order to synthesize poly-(fluorinated alkanesulfonamides) a series of model experiments were carried out: (1) reactions of fluorinated alkanesulfonyl fluorides with amines, (2) reactions of fluorinated alkanesulfonyl chloride with amines and (3) reactions of sodium salts of fluorinated alkanesulfonamides with alkyl iodides of fluorinated alkanesulfonic acid esters. Seventeen new fluorinated alkanesulfonamides were prepared in good yields, namely: RFO(CF2)2SO2NR1R2 (1a-h), R1R2NSO2RFSO2NR1R2 (2a-h) and [Cl (CF2)4O(CF2)2SO2NH(CH2)3]2 (3). Reaction of RFSO2NH2 with equivalent amount of NaOCH3 and methyl iodide was shown to give both the N-mono- and N,N-di-substituted amides. Consequently the N-monosubstituted alkanesulfonamides were chosen as monomers for syntheses of the poly-(fluorinated alkanesulfonamides) and two new polymers were synthesized. The effect of the condition of the polycondensation on M̄n of the polymers were discussed and elemental composition, 19F NMR, IR, M̄n, Tg, tensile strength, thermal and chemical stabilities of the polymers were measured. Several new perfluoroalkanesulfonyl chlorides CISO2RFSO2Cl (4a-c) and fluorinated alkanesulfonic acid esters (6a-d) were synthesized. However, reaction of CFCl2CF2O(CF2)2SO2F with AlCl3 was found to give Cl3CCF2O(CF2)2SO2F (5) instead of the expected sulfonyl chloride.

On perfluoroalkanesulfonyl hydroxylamines

Experiments in order to obtain R fSO 2 substituted hydroxylamines are described. Especially, the reactions of perfluoroalkanesulfonyl chlorides and fluorides with hydroxylamines and the reactions of CH 3SO 2 and/or CH 3 substituted hydroxylamines with elemental fluorine are discussed.