354-25-6Relevant academic research and scientific papers
Unimolecular reactions in the CF3CH2Cl ? CF 2ClCH2F system: Isomerization by interchange of Cl and F atoms
Enstice, Erin C.,Duncan, Juliana R.,Setser,Holmes, Bert E.
experimental part, p. 1054 - 1062 (2011/04/18)
The recombination of CF2Cl and CH2F radicals was used to prepare CF2ClCH2F* molecules with 93 ± 2 kcal mol-1 of vibrational energy in a room temperature bath gas. The observed unimolecular reactions in order of relative importance were: (1) 1,2-ClH elimination to give CF2=CHF, (2) isomerization to CF 3CH2Cl by the interchange of F and Cl atoms and (3) 1,2-FH elimination to give E- and Z-CFCl=CHF. Since the isomerization reaction is 12 kcal mol-1 exothermic, the CF3CH2Cl* molecules have 105 kcal mol-1 of internal energy and they can eliminate HF to give CF2=CHCl, decompose by rupture of the C-Cl bond, or isomerize back to CF2ClCH2F. These data, which provide experimental rate constants, are combined with previously published results for chemically activated CF3CH2Cl* formed by the recombination of CF3 and CH2Cl radicals to provide a comprehensive view of the CF3CH2Cl* ? CF 2ClCH2F* unimolecular reaction system. The experimental rate constants are matched to calculated statistical rate constants to assign threshold energies for the observed reactions. The models for the molecules and transition states needed for the rate constant calculations were obtained from electronic structures calculated from density functional theory. The previously proposed explanation for the formation of CF2=CHF in thermal and infrared multiphoton excitation studies of CF3CH 2Cl, which was 2,2-HCl elimination from CF3CH 2Cl followed by migration of the F atom in CF3CH, should be replaced by the Cl/F interchange reaction followed by a conventional 1,2-ClH elimination from CF2ClCH2F. The unimolecular reactions are augmented by free-radical chemistry initiated by reactions of Cl and F atoms in the thermal decomposition of CF3CH2Cl and CF 2ClCH2F.
A mild hydrodehalogenation of fluoroalkyl halides
Zhang, Cheng-Pan,Chen, Qing-Yun,Xiao, Ji-Chang,Gu, Yu-Cheng
experimental part, p. 671 - 673 (2009/12/22)
A mild hydrodehalogenation reaction of fluoroalkyl halides (RfCF2X, X = Br, I) has been developed under weakly basic conditions, giving the corresponding hydrogenolysis products with moderate to high yields.
Functionalized Copolymers of Terminally Functionalized Perfluoro (Alkyl Vinyl Ether) Reactor Wall for Photochemical Reactions, Process for Increasing Fluorine Content in Hydrocaebons and Halohydrocarbons and Olefin Production
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Page/Page column 5, (2008/06/13)
A photochemical reaction apparatus including a reactor and a light source situated so that light from the light source is directed through a portion of the reactor wall is disclosed. The apparatus is characterized by the portion of the reaction wall comprising a functionalized copolymer of a terminally functionalized perfluoro(alkyl vinyl ether). Also described is a photochemical reaction process using said reactor. The functional group of the copolymer of the apparatus and the process is selected from —SO2F, —SO2CI, —SO3H, —CO2R (where R is H or C1-C3 alkyl), —PO3H2, and salts thereof. A process for increasing the flourine content of at least one compound selected from hydrocarbons and halohydrocarbons, comprising: (a) photochlorinating said at least one compound, and (b) reacting the halogenated hydrocarbon in (a) with HF. A process for producing an olefinic compound, comprising: (a) photochlorinating at least one compound selected from hydrocarbons and halohydrocarbons containing at least two carbon atoms and at least two hydrogen atoms to produce a halogenated hydrocarbon containing a hydrogen substituent and a chlorine substituent on adjacent carbon atoms; and (b) subjecting the halogenated hydrocarbon produced in (a) to dehydrohalogenation.
PHOTOCHLORINATION AND FLUORINATION PROCESS FOR PREPARATION OF FLUORINE-CONTAINING HYDROCARBONS
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Page/Page column 12, (2008/06/13)
A process is disclosed for increasing the fluorine content of at least one compound selected from halohydrocarbons and hydrocarbons. The process involves (a) directing light from a light source through the wall of a reactor to interact with reactants comprising chlorine and said at least one compound in said reactor, thereby producing a halogenated hydrocarbon having increased chlorine content by photochlorination, and (b) reacting said halogenated hydrocarbon produced by the photochlorination in (a) with HF; and is characterized by the light directed through the reactor wall being directed through a poly(perhaloolefin) polymer.
PYROLYSIS PROCESS
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Page/Page column 4, (2008/06/13)
The present invention relates to the pyrolysis of hydrochlorofluorocarbons to form fluoromonomers such as tetrafluoroethylene, the pyrolysis being carried out in a reaction zone lined with nickel and mechanically supported by a jacket of other corrosion resistant metal, the nickel lining providing an improved yield of valuable reaction products.
Process for activation of AIF3 based catalysts and process for isomerising hydrochlorofluorocarbons
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Page 7-8, (2008/06/13)
An activated AlF3 based catalyst is produced by treating a crude AlF3 for more than 5 hours with a gas stream at a temperature from 300°C to 450°C.
Process for preparing fluorohalogenethers
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Page column 9, (2008/06/13)
A process for preparing (per) fluorohalogenethers having general formula (I):(R)nC(F)mOCAF-CA'F2 wherein:A and A', equal to or different the one from the other, are Cl or Br or one is selected from A and A' and hydrogen and the other is halogen selected from Cl, Br; R = F, or a fluorinated, preferably perfluorinated, substituent, selected from the following groups: linear or branched C1-C20 alkyl more preferably C1-C10; C3-C7 cycloalkyl; aromatic, C6-C10 arylalkyl, alkylaryl; C5-C10 heterocyclic or alkylheterocyclic; when R is fluorinated or perfluorinated alkyl, cycloalkyl, arylalkyl, alkylaryl, it can optionally contain in the chain one or more oxygen atoms;when R is fluorinated it can optionally contain one or more H atoms and/or one or more halogen atoms different from F:n is an integer and is 1 or 2; m = 3-n; by reaction of carbonyl compounds having formula (II):(R)pC(F)q(O) wherein:p is an integer and is 1 or 2; q is an integer and is zero or 1, R is as above; in liquid phase with elemental fluorine and with olefinic compounds having formula (III):CAF=CA'F wherein A and A' are as above, at temperatures in the range from -120°C to -20°C.
Process for preparing fluorohalogenethers
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Page 4-5, (2008/06/13)
A process for preparing (per)fluorohalogenethers having general formula (I): (R)nC(F)mOCAF—CA′F2??(I) wherein: A and A′, equal to or different the one from the other, are Cl or Br or one is selected from A and A′ and hydrogen and the other is halogen selected from Cl, Br; R═F, or a fluorinated, preferably perfluorinated, substituent, selected from the following groups: linear or branched C1-C20 alkyl more preferably C1-C10; C3-C7 cycloalkyl; aromatic, C6-C10 arylalkyl, alkylaryl; C5-C10 heterocyclic or alkylheterocyclic; when R is fluorinated or perfluorinated alkyl, cycloalkyl, arylalkyl, alkylaryl, it can optionally contain in the chain one or more oxygen atoms; when R is fluorinated it can optionally contain one or more H atoms and/or one or more halogen atoms different from F: n is an integer and is 1 or 2; m=3-n; by reaction of carbonyl compounds having formula (II): (R)pC(F)q(O)??(II) wherein: p is an integer and is 1 or 2; q is an integer and is zero or 1, R is as above; in liquid phase with elemental fluorine and with olefinic compounds having formula (III): CAF═CA′F??(III) wherein A and A′ are as above, at temperatures in the range from ?120° C. to ?20° C.
PROCESS FOR THE PREPARATION OF 1,1,1,2,2-PENTAFLUOROETHANE
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Page 13-14, (2008/06/13)
A process for the preparation of pentafluoroethane is disclosed which involves contacting a mixture comprising hydrogen fluoride and at least one one starting material selected from haloethanes of the formula CX3191CHX2 and haloethenes of the formula CX2=CX2, where each X is independently selected from the group consisting of F and Cl (provided that no more than four of X are F), with a fluorination catalyst in a reaction zone to produce a product mixture comprising HF, HCl, pentafluoroethane, underfluorinated halogenated hydrocarbon intermediates and less than 0.2 mole percent chloropentafluoroethane based on the total moles of halogenated hydrocarbons in the product mixture. The process is characterized by the fluorination catalyst comprising (i) a crystalline cobalt-substituted alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt (Co+3) and/or (ii) a fluorinated crystalline oxide of (i).
Selective reduction of halopolyfluorocarbons by organosilicon hydrides
Petrov, Viacheslav A.
, p. 7294 - 7297 (2007/10/03)
It is demonstrated that silicon hydrides can be used for reduction of polyfluorinated halocarbons. For example, the reaction between CF3CCl2F and excess triethylsilane, catalyzed by benzoyl peroxide, leads to the formation of a mixture containing CF3CHClF (major), CF3CH2F, and ClSi(C2H5)3. On the other hand, the reaction of chlorofluoroalkanes, containing an internal -CCl2- group readily proceeds with reduction of both chlorines, leading to compounds such as (CF3)2CH2 and CF3CH2C2F5. In contrast to chlorofluoroalkanes, bromofluoroalkanes are much more reactive and reaction with hydrosilane rapidly proceeds without the catalyst at elevated temperature.
