Reaction of phosphorus-containing cyanoguanidines with hexafluoroacetone imines

Substituted hexafluoroacetone imines react with 1-(2-cyanoguanidino) alkylphosphonates at the CN group at –5-0°C, forming [2+4]-cycloaddition products, which are phosphorus-containing 4,4-bis(trifluoromethyl)1,3,5-oxadiazines. The reaction products are readily alkylated by substituted hexafluoroacetone imines at the nitrogen atom of the guanidine fragment. The two reactions are accompanied by tautomeric transformations of the guanidine fragment of the molecules. An NMR spectral analysis was carried out.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2815–2819, December, 1989.     

C-alkylation of 3-methyl-1-phenyl-5-pyrazolone by hexafluoroacetone and its imines

Conclusions Regiospecificity was demonstrated for C-alkylation in the reactions of 3-methyl-1-phenyl-5-pyrazolone with hexafluoroacetone and the trifluoroacetylimine and benzenesulfonylimine of hexafluoroacetone at C⁴ of the heterocycle.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 684–686, March, 1987.     

Photodifluoramination of nitriles

Gas phase irradiation of N₂F₄(NF₂) in the presence of trifluoroacetonitrile, ¹⁵N-trifluoroacetonitrile, or acetonitrile resulted in the formation of products that correspond to perfluorination of the unsaturation or to conversion of the substrate to a saturated fluorocarbon. The proposed mechanism involves atomic fluorine attack on the nitrile and subsequent rearrangement of the resulting N,N-difluorohydrazone, R₂C(F)NNF₂, to an alkylfluorodiazene R₂C(F)-N=N-F. Decomposition of diazenes accounts for the observed products.     

Fluorine-containing imines. Communication 6. Reaction of hexafluoroacetone perfluoropivaloylimine with dimethylantline and dimethylbenzylamine

Conclusions Hexafluoroacetone perfluoropivaloylimine reacts with dimethylaniline as a C-alkylating agent and with dimethyIbenzylimine and triethylamine as a hydride-ion acceptor: the reactions are accompanied by the ejection of perfluoro-tert-butyl anions, which leads to the formation of isocyanates.See [1] for Communication 5.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2022–2024, September, 1987.     

Fluorine-containing imines. 5. Reactions of acylimines of hexafluoroacetone and perfluoroalkyl isocynates with methylenebisdimethylamine

Conclusions In reactions with hexafluoroacetone acylimines, perfluoroalkyl isocyanates and imidoyl fluoride, methylenebisdimethylamine serves a source of dimethylaminomethylene, hydride ion, and dimethylamino group.For communication 6, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1814–1817, August, 1987.     

N-benzoylimine of hexafluoroacetone

Conclusions The N-benzoylimine of hexafluoroacetone is considerably more active than the imine of hexafluoroacetone in reaction with nucleophilic reagents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2046–2048, November 1965     

Physical properties of hexafluoroacetone

The vapour pressure of hexafluoroacetone has been determined from 58°C to the critical point. The critical temperature and pressure were also measured. Densities of the liquid and saturated vapour were determined between - 50°C and the critical point. Using this information the rectilinear diameter line and the heats of vaporization have been determined.     

Reaction of hexafluoroacetone with azacyclohexanes

Conclusions Piperidine and its C-methyl derivatives are aromatized by hexafluoroacetone with simultaneous C-alkylation at one or both of the -positions of the ring, and in the case of - and -methylpyridines also at the CH₃ group.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1652–1656, July, 1989.     

Reductive defluorination of hexafluoroacetone anil

Hexafluoroacetone anil smoothly adds methyllithium at the C=N bond but undergoes reductive defluorination upon the action of Grignard reagents or metallic zinc to give 2-phenylaminopentafluoropropylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 202–205, January, 1990.     

A pinacone from hexafluoroacetone

Conclusions The reaction of hexafluoroacetone with triethyl phosphite was investigated, and dodecafluoropinacone was synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8 pp. 1526–1528, August, 1964     

Reactions of diarylamines with hexafluoroacetone

Diphenylamine reacts with hexafluoroacetone to give a mixture of products, of which 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)diphenylamine (II) was isolated. N-Arylanthranilic acids modify the 1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group upon the reaction of its sodium salt with the hydrate of hexafluoroacetone (I) under mild conditions. This method gave 4-(1-hydroxy-1-trifluoromethyl-2,2,3-trifluoroethyl)-N-(2,3-xylyl)anthranilic acid from N-(2,3-xylyl)anthranilic acid in 93% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 952–954, April, 1991.