A. I. Rapkin

Some reactions of chlorine and iodine fluorosulfates

Abstract The behaviour of ClOSO 2 F towards acetylene and the CN bond of perfluorocarbon acid nitriles as well as a possibility of CN bond cleavage in perfluoronitroso compounds were studied. Investigation of the chlorinating activity of ClOSO 2 F was continued. The addition reactions of IOSO 2 F to double bonds of fluoroolefines as well as the reactions of S 2 O 6 F 2 with ethylnitrobenzenes were realized.

Geminal (difluoroamino)nitro compounds

A novel preparative method for the synthesis of geminal (difluoroamino)nitro compounds was developed, The method involves the reaction ofN,N-difluoro-O-fluorosulfonyl- hydroxylamine with the corresponding salts of nitro compounds, Dependences of the yields of (difluoroamino)nitro compounds on the reaction conditions, the nature of the cation in the salts, and the properties of solvents were studied.

Reactions of fluoroolefins with halogens in strong acid medium

Conclusions1.In the reactions of tetrafluoroethylene and hexafluoropropylene in a HSO3F/SbF5 medium, a joint addition of both halogen and the fluorosulfate group to the multiple bond of the fluoroolefin takes place with the formation of the corresponding 2-haloperfluoroalkyl fluorosulfates.2.Under mild conditions, hexafluoropropylene reacts with the superacid HSO3/SbF5 to form 2-hydrohexafluoropropyl fluorosulfate and 2-hydrohexafluoropropane.

Some properties of polyfluoroacyl- and polyfluoroacetonyl fluorosulfates

ConclusionsPolyfluoroacyl fluorosulfates are decomposed by the action of KF, SbF5 and its mixtures with HSO3F with the formation of the corresponding acyl fluorides. Pentafluoroacetonyl fluorosulfate reacts with SbF5 to form hexafluoroacetone; the fluoride ion causes decomposition of 3-chlorotetrafluoroacetonyl fluorosulfate to chlorodifluoroacetyl fluoride.

Reaction of 1,1,2-trifluoro-2-chloroethyldiethylamine with fluorocarboxylic acids

ConclusionsThe corresponding acyl fluorides are formed as the result of reacting 1,1,2-trifluoro-2-chloroethyldiethylamine with fluorocarboxylic acids.

Reaction of polyfluoroalkyl fluorosulfates with N-nucleophiles

Conclusions1.Polyfluoroalkyl fluorosulfates react with hydrazines and ammonia to form hydrazines and amides of the corresponding polyfluorocarboxylic acids.2.Treatment of ethereal solutions of β-iodo- and β-bromooctafluoroisobutyl fluorosulfates by ammonia leads to the halogenation of the ester and formation of the ethyl ester of α-hydrohexafluoroisobutyric acid, and correspondingly, ethyl iodide or ethyl bromide.

Reactions of chlorine and bromine fluorosulfates with perfluoroalkyl halides in a strongly acidic medium

Conclusions1.Chlorine fluorosulfate is more active than bromine fluorosulfate in the substitution reaction of halogen atom in alkyl halides by the fluorosulfate group.2.In a fluorosulfonic acid medium containing antimony pentafluoride, the reaction with chlorine fluorosulfate leads to the substitution of the primary chlorine atom in perfluoro-alkyl chlorides, and also the primary and secondary bromine atoms in perfluoroalkyl bromides by the fluorosulfate group under mild conditions.

Reaction of α,α,ω-trihydroperfluoroalkyl esters of phosphorous acid with polyfluorocarbonyl compounds

Conclusions1.The α,α,ω-trihydroperfluoroalkyl esters of phosphorous acid react with polyfluorocarbonyl compounds the same as unfluorinated phosphites, but exhibit a lower reactivity.2.The reaction of tris (1,1,3-trihydroperfluoropropyl) phosphite with the hydrates of hexafluoroacetone and trifluoroacetaldehyde respectively givesα-monohydroperfluoroisopropyl bis (1,1,3-trihydroperfluoropropyl) phosphate and 2,2,2-trifluoroethyl bis (1,1,3-trihydroperfluoropropyl) phosphate.

Synthesis and some properties of 5-fluorodinitromethyl- and 5-difluoronitromethyltetrazoles

Conclusions1.The synthesis and study of some properties of 5-fluorodinitromethyltetrazole and of 5-difluoronitro-methyltetrazole has been carried out.2.Tetrazoles and their salts are alkylated predominantly in position 2.

Certain reactions of tris(α,α,ω-trihydroperfluoroalkyl) phosphites

ConclusionsCertain properties of tris(1,1,3-trihydroperfluoropropyl), tris(1,1,5-trihydroperfluoropentyl), and tris(1,1,7-trihydroperfluoroheptyl) phosphites were studied, and it was shown that the presence of theα,α,ω-trihydroperfluoroalkoxyl groups determines their behavior as the result of an increase in the v-acceptor and decrease in the n-donor ability of the phosphorus atom.