355-02-2Relevant articles and documents
THE VAPOUR PRESSURES AND EXCESS FREE ENERGIES OF MIXING OF THE SYSTEMS HEXAFLUOROBENZENE-CARBON TETRACHLORIDE AND HEXAFLUOROBENZENE-PERFLUOROMETHYLCYCLOHEXANE
Patrick, C. R.,Tomes, F.
, p. 267 - 278 (1980)
The vapour pressures of liquid mixtures of hexafluorobenezene with carbon tetrachloride and of hexafluorobenzene with perfluoromethylcyclohexane (tetradecafluoromethylcyclohexane) have been measured in the range of temperature 20-50 deg C, in a static system.These have been used to obtain the excess free energies of the mixtures.Both mixtures show large positive deviations from thermodynamic ideality, and also show azeotropic behaviour.
Prevention of anode fouling during the electrochemical perfluorination of aromatic carboxylic acid chlorides
Ilayaraja,Velayutham,Noel
experimental part, p. 656 - 661 (2009/12/22)
The electrochemical perfluorination of benzoyl chloride, p-substituted benzoyl chlorides and cyclo-hexane carboxylic acid chloride in anhydrous hydrogen fluoride (AHF) medium on nickel electrode is reported. Experimental conditions suppressing polymeric f
Electrochemical fluorination of toluene and benzotrifluoride in the presence of triallylamine
Matalin,Kaurova,Berenblit,Gribel'
, p. 2090 - 2092 (2008/09/17)
Electrochemical fluorination of benzotrifluoride in the presence of triallylamine as depolarizer was studied. The possibility of preparing perfluoromethylcyclohexane and its isomers with high current efficiency and substance yield in combination with perfluorinated tertiary amines was examined.
Electrochemical fluorination of unsaturated sulfides and sulfones
Grigor'eva,Shainyan,Kaurova,Gracheva,Lesnevskaya,Barabanov
, p. 1095 - 1100 (2007/10/03)
Electrochemical fluorination of some unsaturated sulfides and sulfones and their reactions with anhydrous HF were studied.
DIRECT GAS-PHASE CATALYTIC FLUORINATION OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
Zakharov, V. Yu.,Denisov, A. K.,Novikova, M. D.
, p. 1942 - 1945 (2007/10/03)
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.
FLUORINATIONS WITH POTASSIUM TETRAFLUOROCOBALTATE. PART VIII. FLUORINATIONS OF TOLUENE AND OF PHENYLACETIC ACID
Bailey, John,Plevey, Raymond G.,Tatlov, John Colin
, p. 23 - 38 (2007/10/02)
At 340 deg C, toluene gave five 1-trifluoromethyl-substituted compounds: -2H,4H,5H-tetrafluorocyclohexa-1,4-diene (IX); -2H-4H/5H-hexafluorocyclohex-1-ene (X); -2H-octafluorocyclohex-1-ene (IV); -nonafluorocyclohex-1-ene (III); also perfluoromethylcyclohexane (II): traces of perfluorocyclohexane (I) were found.The 1-difluoromethyl-substituted analogues of these five were also obtained: - compounds XII, XV, VIII, VI, and V, respectively.A further five 1-difluoromethyl-substituted derivatives were found : -nonafluorocyclohex-3-ene (VII); an inseparable mixture of the -2H,4H- and -2H,5H-heptafluorocyclohex-1-enes (XI); -2H-3H/4H-hexafluorocyclohex-1-ene (probably) (XIV); and (difluoromethyl)benzene (XIII). Structures of the unknown products were established by analysis and by nmr and ir spectroscopy.Further, the key intermediate (XII) was oxidized to difluoromalonic acid, whilst compound IV was dehydrofluorinated, to give 2H-(difluoromethyl)tetrafluorobenzene (XXI), together with an inseparable mixture of 2H,4H- and 2H,5H-1-(difluoromethyl)pentafluorocyclohexa-1,4-diene (XX).Dehydrofluorination of mixed heptafluoro-enes XI afforded 2H-1-(difluoromethyl)hexafluorocyclohexa-1,4-diene (XVIII), and mixed 2H-1- and 1H-2-(difluoromethyl)hexafluorocyclohexa-1,3-diene (XIX). Difluoromethylundecafluorocyclohexane (V) did not dehydrofluorinate.Phenylacetic acid was fluorinated likewise, and gave a similar range of products, but also one (originally an acid fluoride?) which was converted to the methyl ester of tridecafluoro(cyclohexylacetic) acid (XVII).The probable pathway of the fluorination process could be worked out.
FLUOROCYCLOHEXANES. PART XVII. DEHYDROFLUORINATIONS OF THE CIS AND THE TRANS ISOMERS OF 2H-1-(DIFLUOROMETHYL)DECAFLUOROCYCLOHEXANE
Bailey, John,Plevey, Raymond G.,Tatlow, John Colin
, p. 227 - 234 (2007/10/02)
2H-1-(Difluoromethyl)octafluorocyclohex-1-ene (I) and cobalt trifluoride at 165 deg C afforded 2H-1-(trifluoromethyl)octafluorocyclohex-1-ene (IV) and four decafluorocyclohexane derivatives: the cis (III), and trans (V), 2H-1-(trifluoromethyl)-; the cis (VII), and trans (VI), 2H-1-(difluoromethyl) compounds.Dehydrofluorination of VII, using aqueous potassium hydroxide, gave only one alkene, 1-(difluoromethyl)nonafluorocyclohex-1-ene (VIII).In a slower reaction VI afforded two alkenes, mainly VIII, but also an isomer, 1-(difluoromethyl)nonafluorocyclohex-2-ene (IX) (ratio 2:1).
FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 9. FLUORINATIONS OF TOLUENE AND XYLENE DERIVATIVES BY MEANS OF CAESIUM TETRAFLUOROCOBALTATE(III)
Bailey, John,Plevey, Raymond G.,Tatlow, John Colin
, p. 1 - 14 (2007/10/02)
Benzotrifluoride at 320 deg C afforded some m-fluorobenzotrifluoride and octafluorotoluene (III), together with perfluoromethylcyclohexane (I), and also traces of 2H-heptafluorotoluene and 1-trifluoromethylnonafluorocyclohex-1-ene.Toluene itself gave (difluoromethyl)benzene, fluoro- and difluoro-methylpentafluorobenzene, difluoromethylundecafluorocyclohexane and (I); also traces of di- and tri-fluoromethylnonafluorocyclohex-1-ene: no benzotrifluoride or (III) were detected. 1,3-Bis(trifluoromethyl)benzene at 420 deg C gave 4,5,6-trifluoro-1,3-bis(trifluoromethyl)benzene, decafluoro-1,3-dimethylbenzene, and perfluoro-1,3-dimethylcyclohexane.Para-xylene at 350 deg C afforded 1,4-bis(difluoromethyl)tetrafluorobenzene, 1-difluoromethyl-4-trifluoromethyltetrafluorobenzene, decafluoro-1,4-dimethylbenzene (XIX), and perfluoro-1,4-dimethylcyclohexane (XVIII).Defluorination occurred to a significant extent on passage of the saturated cyclic fluorocarbons (I) and (XVIII) over the fully spent fluorinating agent (presumably caesium trifluorocobaltate) at ca. 400 deg C; the fluorocarbon arenes, (III) and (XIX) respectively, were obtained.
Electron Affinities from Electron-Transfer Equilibria : A(-) + B = A + B(-)
Grimsrud, Eric P.,Caldwell, Gary,Chowdhury, Swapan,Kebarle, Paul
, p. 4627 - 4634 (2007/10/02)
Determination of the equilibrium constants K1 for gas-phase electron-transfer equilibria with a pulsed electron beam high ion source pressure mass spectrometer led to the electron affinities of 34 compounds with EA's between 0.5 and 3eV.The compounds are mostly substituted nitrobenzenes, substituted quinones, and conjugated molecules containing oxygen atoms.The EA of smaller molecules like SO2, NO2, CS2, and CH3NO2 also were determined.The method is very well suited for rapid, accurate, routine determinations of electron affinities.A comparison with EA's determined with other gas-phase methods and EA's evaluated from polarographic half-wave reduction potentials and charge-transfer spectra in solution is made.The rate constants for a number of exothermic electron-transfer reactions were determined.Most of these proceed at near collision rates.Electron-transfer reactions involving perfluorinated compounds like perfluoromethylcyclohexane, perfluorocyclohexane, and sulfurhexafluoride do not follow this behavior.While the perfluoro compounds have high thermal electron capture cross sections, they do not accept electrons from A(-) of compounds A with lower electron affinity.The perfluoro anions do transfer electrons to compounds A with higher electron affinity, and the rate constants increase with EA(A) - EA(perfluoro compound).
Electron affinity of SF6 and perfluoromethylcyclohexane. The unusual kinetics of electron transfer reactions A- + B = A + B-, where A = SF6 or perfluorinated cyclo-alkanes
Grimsrud, E. P.,Chowdhury, S.,Kebarle, P.
, p. 1059 - 1068 (2007/10/02)
Measurements of the equilibria ( 1 ): A- + B = A + B- with a pulsed electron high pressure mass spectrometer lead to ΔG, ΔH, and ΔS.Equilibria involving SF6 as A and perfluoromethylcyclohexane C7F14 provide electron affinities E.A.(SF6) =1.05 +/- 0.1 eV and E.A.(C7F14) =1.06 +/- 0.15 eV.The kinetics of reactions (1) involving the above two compounds were studied.The rate constants kj for SF6- + B = SF6 + B- were found to increase with exothermicity of the reaction.The temperature dependence for k f was determined.B compounds leading to high exothermicities were associated with kj at the collision limit and essentially no temperature dependence.B of progressively lower electron affinity led to kf below the collision limit and negative temperature dependence, while B with the lowest E.A. but still leading to exothermic reaction produced lowest kf with positive temperature dependence.A model is provided explaining the above behavior.The known large change of geometry between SF6- and SF6 introduces an internal barrier in the reaction coordinate for the reactions ( 1 ) involving SF6.
