865-71-4Relevant articles and documents
Skeletal Rearrangements during the Fluorination of C6-Hydrocarbons over Cobalt(III) Trifluoride
Burdon, James,Creasey, Jeremy C.,Proctor, Lee D.,Plevey, Raymond G.,Yeoman, J.R. Neil
, p. 445 - 447 (2007/10/02)
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.
REACTIONS OF TETRAFLUOROETHYLENE OLIGOMERS. PART 1. SOME PYROLYTIC REACTIONS OF THE PENTAMER AND HEXAMER AND OF THE FLUORINE ADDUCTS OF THE TETRAMER AND PENTAMER
Coe, Paul L.,Sellers, Simon F.,Tatlow, John Colin
, p. 417 - 440 (2007/10/02)
Pyrolyses of these highly branched fluorocarbons over glass beads caused the preferential thermolyses of C-C bonds where there is maximum carbon substitution.Fluorinations of perfluoro-3,4-dimethylhex-3-ene (tetramer) (I) and perfluoro-4-ethyl-3,4-dimethylhex-2-ene (pentamer) (II) over cobalt (III) fluoride at 230 deg C and 145 deg C respectively afforded the corresponding saturated fluorocarbons (III) and (IV), though II gave principally the saturated tetramer (III) at 250 deg C.Pyrolysis of III alone at 500-520 deg C gave perfluoro-2-methylbutane (V), whilst pyrolysis of III in the presence of bromine or toluene afforded 2-bromononafluoorobutane (VI) and 2H-nonafluorobutane (VII) respectively.Pyrolysis of perfluoro-3-ethyl-3,4-dimethylhexane (IV) alone gave a mixture of perfluoro-2-methylbutane (V), perfluoro-2-methylbut-1-ene (VIII), perfluoro-3-methylpentane (IX), perfluoro-3,3-dimethylpentane (X), and perfluoro-3,4-dimethylhexane (III).Pyrolysis of IV in the presence of bromine gave (VI) and 3-bromo-3-trifluoromethyldecafluoropentane (XI): with toluene, pyrolysis gave VII and 3H-3-trifluoromethyldecafluoropentane (XII).Pyrolysis of II at 500 deg C over glass gave perfluoro-1,2,3-trimethylcyclobutane (XIII) and perfluoro-2,3-dimethylpenta-1,3(E)- and (Z)-diene (XIV) and (XV) respectively.The diene mixture (XIV and XV) was fluorinated with CoF3 to give perfluoro-2,3-dimethylpentane (XVI) and was cyclised thermally to give the cyclobutene (XIII).Pyrolysis of perfluoro-2-(1'-ethyl-1'-methylpropyl)-3-methylpent-1-ene (XVII) (TFE hexamer major isomer) at 500 deg C gave perfluoro-1-methyl-2-(1'-methylpropyl)cyclobut-1-ene (XVIII) and perfluoro-2-methyl-3-(1'-methylpropyl)buta-1,3-diene (XIX).Fluorination of XVIII over CoF3 gave perfluoro -1-methyl-2-(1'-methylpropyl)cyclobutane (XX), which on co-pyrolysis with bromine gave VI.XIX on heating gave XVIII.Reaction of XVIII with ammonia in ether gave a mixture of E and Z 1-trifluoromethyl-2-(1'-trifluoromethylpentafluoropropyliden-1'-yl)tetrafluorocyclobutylamine (XXI) which on diazotisation and hydrolysis afforded 2-(2'trifluoromethyltetrafluorocyclobut-1-en-1'-yl)-octafluorobutan-2-ol (XXII).
