31665-17-5Relevant academic research and scientific papers
The Preparation and Characterization of Radical Cation Salts Derived from Perfluorobenzene, Perfluorotoluene, and Perfluoronaphthalene
Richardson, T. J.,Tanzella, F. L.,Bartlett, Neil
, p. 4937 - 4943 (2007/10/02)
The salts C6F6+AsF6- (yellow), C6F5CF3- (lime green), and C10F8+AsF6- (dark green) may be prepared by electron oxidation of the appropriate perfluoro aromatic molecule with O2+AsF6-.Other O2+ salts can be similarly employed as can the more strongly oxidizing transition-metal hexafluorides, but salts of the latter are more labile than their AsF- relatives.C6F6+AsF6- is a convenient electron oxidizer (C6F6AsF6+C10F8 -> C10F8AsF6+C6F6) since that which remains from the reaction decomposes at room temperature to volatile products (2C6F6AsF6 -> C6F6+1,4-C6F8+2AsF5).Magnetic susceptibilities for C6F6AsF6 and C10F8AsF6 approximate to Curie law behavior, and g values are close to free-electron values.X-ray diffraction data (single crystal) show C6F6AsF6 to be primitive rhombohedral with a0=6.60 (1) Angstroem, α=106.0 (1) deg, V=246.1 Angstreom3, Z=1, probable space group R3, and (powder data) C10F8AsF6 to be tetragonal with a0=8.27 (5) Angstroem, c0=18.57 (s) Angstroem, V=1270 Angstoem3, Z=4.Salts derived from the monocyclic perfluoro aromatics are thermally unstable but can be kept below -15 deg C.The perfluoronapthalene salts are indefinitely stable at room temperatures.All hydrolyze rapidly.The products of thermal decomposition of the hexafluoroarsenates of the monocyclic cation salts parallel the products of the attack by F-.The latter reaction products are in the molar ratios indicated by the following equations: 2C6F6+ 2F- -> C6F6+ 1,4-C6F8; 2C6F5CF3+ ->2F- -> C6F5CF3+1,3-C6F7CF3.The 1,3-C6F7CF3 isomerizes to a 1:1 mixture with 1,4-C6F7CF3 over several days in the presence of fluoro acids.Mechanisms for the formation of the dienes are discussed.
FLUORINATION OF POLYFLUOROAROMATIC COMPOUNDS WITH VANADIUM PENTAFLUORIDE
Bardin, V. V.,Avramenko, A. A.,Furin, G. G.,Yakobson, G. G.,Krasilnikov, V. A.,et al.
, p. 37 - 46 (2007/10/02)
Fluorination of polyfluoro-derivatives of benzene and diphenyl with vanadium pentafluoride at -25 to -10 deg C afforded fluorinated cyclohexadienes and cyclohexenes.Octafluoronaphthalene was converted under these conditions to perfluoro-1,4-dihydronaphthalene, perfluorotetralin, perfluoro-1,4,5,8-tetrahydronaphthalene and perfluoro-1,2,3,4,5,8-hexahydronaphthalene.
AROMATIC FLUORINE DERIVATIVES. XCVII. OXIDATIVE FLUORINATION OF PERFLUORINATED AROMATIC COMPOUNDS WITH VANADIUM PENTAFLUORIDE
Bardin, V. V.,Furin, G. G.,Avramenko, A. A.,Krasil'nikov, V. A.,Tushin, P. P.,et all
, p. 307 - 311 (2007/10/02)
Perfluorinated aromatic compounds are converted by the action of vanadium pentafluoride at -25 to -15 deg C into perfluorinated derivatives of cyclohexadiene and cyclohexene.The rate of addition of the two fluorine atoms to the perfluorinated derivatives of 1,3- and 1,4-cyclohexadiene under conditions of competing fluorination depends on the nature of the substituent at the carbon-carbon double bond.
