- Explored routes to unknown polyfluoroorganyliodine hexafluorides, R FIF6
-
Two routes to RFIF6 compounds were investigated: (a) the substitution of F by RF in IF7 and (b) the fluorine addition to iodine in RFIF4 precursors. For route (a) the reagents C6F5SiMe3, C6F 5SiF3, [NMe4][C6F 5SiF4], C6F5BF2, and 1,4-C6F4(BF2)2 were tested. C 6F5IF4 and CF3CH2IF 4 were used in route (b) and treated with the fluoro-oxidizers IF7, [O2][SbF6]/KF, and K2[NiF 6]/KF. The observed sidestep reactions in case of routes (a) and (b) are discussed. Interaction of C6F5SiX3 (X = Me, F), C6F5BF2, 1,4-C6F 4(BF2)2 with IF7 gave exclusively the corresponding ring fluorination products, perfluorinated cyclohexadiene and cyclohexene derivatives, whereas [NMe4][C6F 5SiF4] and IF7 formed mixtures of C 6FnIF4 and C6FnH compounds (n = 7 and 9). CF3CH2IF4 was not reactive towards the fluoro-oxidizer IF7, whereas C6F 5IF4 formed C6FnIF4 compounds (n = 7 and 9). C6F5IF4 and CF 3CH2IF4 were inert towards [O 2][SbF6] in anhydrous HF. CF3CH 2IF4 underwent C-H fluorination and C-I bond cleavage when treated with K2[NiF6]/KF in HF. The fluorine addition property of IF7 was independently demonstrated in case of perfluorohexenes. C4F9CFCF2 and IF7 underwent oxidative fluorine addition at -30 °C, and the isomers (CF 3)2CFCFCFCF3 (cis and trans) formed very slowly perfluoroisohexanes even at 25 °C. The compatibility of IF7 and selected organic solvents was investigated. The polyfluoroalkanes CF 3CH2CHF2 (PFP), CF3CH 2CF2CH3 (PFB), and C4F9Br are inert towards iodine heptafluoride at 25 °C while CF3CH 2Br was slowly converted to CF3CH2F. Especially PFP and PFB are new suitable organic solvents for IF7.
- Frohn, Hermann-Josef,Bardin, Vadim V.
-
experimental part
p. 1000 - 1006
(2010/11/16)
-
- Technology for the preparation of perfluoro-organic compounds
-
Fluorination by elemental fluorine of fluorine-containing alkenes, alkanes, ethers and tertiary amines was investigated, aimed at obtaining the perfluorinated analogs. The factors affecting yield of the target compounds were studied. Elements of technology were elucidated.
- Moldavskii, Dmitrii D.,Bispen, Tatjana A.,Kaurova, Galina I.,Furin, Georgii G.
-
p. 157 - 167
(2007/10/03)
-
- DIRECT GAS-PHASE CATALYTIC FLUORINATION OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
-
The fluorination of a wide range of polyfluorinated organic compounds with molecular fluorine in the gas phase in a layer of NiF2/support as catalyst was investigated.It was shown that the selectivity of fluorination of the series of fluoroolefins, acid fluorides, polyfluoroalkanes, and hydrogen-containing ethers can be greatly increased.The developed method was used on an industrial scale in the production of perfluorinated liquids.
- Zakharov, V. Yu.,Denisov, A. K.,Novikova, M. D.
-
p. 1942 - 1945
(2007/10/03)
-
- Promising materials in chemical technology. Synthesis and use of vanadium pentafluoride
-
Features of vanadium pentafluoride synthesis on a semicommercial installation of horizontal type from various vanadium-containing concentrates and wastes have been investigated.Highly corrosive activity of vanadium pentafluoride has been discovered; protective ceramic material based on calcium fluorozirconate has been developed.
- Krasil'nikov, V. A.,Andreev, G. G.,Karelin, A. I.,Guzeeva, T. I.,Furin, G. G.,et al.
-
p. 1657 - 1659
(2007/10/03)
-
- Skeletal Rearrangements during the Fluorination of C6-Hydrocarbons over Cobalt(III) Trifluoride
-
Perfluorination of hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, methylcyclopentane and cyclohexane over cobalt(III) trifluoride gave, in each case except perhaps cyclohexane, a mixture of linear, branched and cyclic C6-fluorocarbons: the degree of skeletal rearrangement (excluding cyclohexane) varied from ca. 7percent (methylcyclopentane) to 96percent (2,2-dimethylbutane).A carbocation mechanism, which does not proceed to equilibrium, is suggested.
- Burdon, James,Creasey, Jeremy C.,Proctor, Lee D.,Plevey, Raymond G.,Yeoman, J.R. Neil
-
p. 445 - 447
(2007/10/02)
-
- FLUORINATION OF POLYHALOGENATED UNSATURATED COMPOUNDS WITH VANADIUM PENTAFLUORIDE
-
Vanadium pentafluoride reacts with polyfluorinated and polychlorinated olefins, alkadienes, cycloalkenes and cyclodienes in CFCl3 or without a solvent at -25 deg C to 100 deg C, forming products of addition of two fluorine atoms across the C=C bond.
- Bardin, V. V.,Avramenko, A. A.,Furin, G. G.,Krasilnikov, V. A.,Karelin, A. I.,et al.
-
p. 385 - 400
(2007/10/02)
-
- Photoinduced Fluorination of Hexafluoropropene Trimers: Synthesis of Branched Perfluoroalkanes
-
Hexafluoropropene trimers, perfluoro-3-ethyl-2,4-dimethylpent-2-ene (1) and perfluoro-3-isopropyl-4-methylpent-2-ene (2) reacted with fluorine under u.v. irradiation to give the new and highly branched perfluoroalkanes perfluoro-2,3,3,4-tetramethylpentane (7) and perfluoro-2,3,4-trimethylpentane (8) through a mechanism involving the elimination-readdition of CF3 groups.Compound (7), which is very bulky, can be easily cleaved at 200 deg C to give two perfluoro radicals capable of initiating the polymerization of vinylic monomers.
- Tonelli, Claudio,Tortelli, Vito
-
-
- REACTION OF POLYHALOGENATED UNSATURATED COMPOUNDS WITH VANADIUM PENTAFLUORIDE
-
Terminal polyhalogenoalkenes are fluorinated by vanadium pentafluoride at -20 to -30 deg C, whereas internal polyfluoroalkenes only react with vanadium pentafluoride when heated. 2-Chloropentafluoro-1,3-butadiene adds fluorine atoms predominantly at positions 1,4 under the influence of vanadium pentafluoride, but only the isomeric tetrafluorohexachlorobutanes are formed from perchloro-1,3-butadiene.Fluorination of perfluoroallylbenzene and perfluoro-β-methylstyrene takes place more rapidly in the side chain than in the aromatic ring.
- Petrov, V. A.,Bardin, V. V.,Furin, G. G.,Avramenko, A. A.,Galakhov, M. V.,et al.
-
-
