- Absolute rates of intermolecular carbon-hydrogen abstraction reactions by fluorinated radicals
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Using competition kinetic methodology, absolute rate constants for bimolecular hydrogen abstraction from a variety of organic substrates in solution have been obtained for the n-C4H9CF2CF2(·), n-C4F9(·), and i-C3F7(·) radicals. Fluorine substitution substantially increases the reactivity of alkyl radicals with respect to C-H abstraction, with the secondary radical being most reactive. A wide range of substrate reactivities (5200-fold) was observed, with the results being discussed in terms of an interplay of thermodynamic, polar, steric, stereoelectronic, and electrostatic/field effects on the various C-H abstraction transition states. Representative carbon-hydrogen bond dissociation energies of a number of ethers and alcohols have been calculated using DFT methodology.
- Shtarev, Alexander B.,Tian, Feng,Dolbier Jr., William R.,Smart, Bruce E.
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Read Online
- Fluorine chemistry. Part 2. Synthesis and characterization of 2H-heptafluoropropane (HFC-227ea)
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A facile method has been developed for the synthesis and characterization of volatile 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a potential non-ozone depleting hydrofluorocarbon substitute for Halon 1301 (CF3Br). The method involves hydrofluorination of hexafluoropropene using in situ generated onium bifluoride obtained from the decomposition of anhydrous tetrabutylammonium fluoride. The reagent acts as an excellent equivalent to hydrogen fluoride and permits the use of normal glassware.
- Bhadury, Pinaki S.,Singh, Sapna,Sharma, Mamta,Malhotra, Ramesh C.,Sekhar, Krishnamurthy
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Read Online
- Unusual conversion of perfluoromethylepoxycyclopentane into a linear β-aminovinylketone by C-C bond cleavage
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2,3,3,4,4,5,5-Heptafluoro-1-trifluoromethyl-1,2-epoxycyclopentane reacted with 2-isopropyl-acetophenone imine giving 2,3,3,4,4,5,5-heptafluoro-2-trifluoromethyl-1-(2′-isopropylimino- 2′-phenylethane) cyclopentan-1-ol, which in its turn underwent an intramolecular rearrangement yielding the linear 4,4,5,5,6,6,7,8,8,8-decafluoro-1-isopropylamino-oct-1-en-3-one, being characterized by X-ray structural analysis (triclinic, P-1, a = 920.5(2), b = 1027.9(3), c = 1127.4(3)pm, α = 110.99, β = 105.68°, γ = 96.75°).
- Barten, Jan A.,Kadyrov, Alexander A.,Roeschenthaler, Gerd-Volker
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Read Online
- A novel and efficient synthetic route to perfluoroisobutyronitrile from perfluoroisobutyryl acid
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A novel synthetic route to perfluoroisobutyronitrile from perfluoroisobutyryl acid which has mild conditions and low toxicity is described. This study introduces detailed synthetic protocols and characterization including GC-MS, 13C NMR and 19F NMR spectroscopy of perfluoroisobutyryl acid, perfluoroisobutyryl chloride, perfluoroisobutyl amide and perfluoroisobutyronitrile. Besides, this route is superior to the established patent and shows potential application in high voltage electrical equipment.
- Wang, Yi,Sun, Mengting,Gao, Zhanyang,Zou, Lilin,Zhong, Lingyu,Peng, Ruichao,Yu, Ping,Luo, Yunbai
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p. 37159 - 37164
(2018/11/26)
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- METHOD AND APPARATUS FOR CONTINUOUSLY PRODUCING 1,1,1,2,3-PENTAFLUOROPROPANE WITH HIGH YIELD
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A method and apparatus for method of continuously producing 1,1,1,2,3-pentafluoropropane with high yield is provided. The method includes (a) bringing a CoF3-containing cobalt fluoride in a reactor into contact with 3,3,3-trifluoropropene to produce a CoF2-containing cobalt fluoride and 1,1,1,2,3-pentafluoropropane, (b) transferring the CoF2-containing cobalt fluoride in the reactor to a regenerator and bringing the transferred CoF2-containing cobalt fluoride into contact with fluorine gas to regenerate a CoF3-containing cobalt fluoride, and (c) transferring the CoF3-containing cobalt fluoride in the regenerator to the reactor and employing the transferred CoF3-containing cobalt fluoride in Operation (a). Accordingly, the 1,1,1,2,3-pentafluoropropane can be continuously produced with high yield from the 3,3,3-trifluoropropene using a cobalt fluoride (CoF2/CoF3) as a fluid catalyst, thereby improving the reaction stability and readily adjusting the optimum conversion rate and selectivity.
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Paragraph 0110-0111
(2014/05/20)
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- Unimolecular rate constant and threshold energy for the HF elimination from chemically activated CF3CHFCF3
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Combination of CF3CHF and CF3 radicals at room temperature generated chemically activated CF3CHFCF3 molecules with 95 ± 3 kcal/mol of internal energy that decompose by loss of HF, initially attached to adjacent carbons, with an experimental unimolecular rate constant of (4.5 ± 1.1) x 102 s-1. Density functional theory was used to model the unimolecular rate constant for HF elimination, kHF, to determine a threshold energy of 75 ± 2 kcal/mol.
- Duncan, Juliana R.,Roach, Michael S.,Stiles, Brooke Sibila,Holmes, Bert E.
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experimental part
p. 6996 - 7002
(2011/02/16)
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- Coupling reactions of chlorofluoro and perfluoroalkyl iodides
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Coupling reactions of chlorofluoro- and perfluoroalkyl iodides R f-I with Rf = ClCF2CFCl-(CF2) 3CF2-, ClCF2CFClO(CF2) 3CF2-, ClCF2CFCl-, (CF3) 2CF- , (CF3)2CFCF2CF2- in the presence of a zinc/solvent system give dimers in good yields. Both homodimerizations (one iodide) and heterodimerizations (two different iodides) have been studied. The effect of temperature and solvent is shown. The zinc mediated dechlorination of vicinal chlorine atoms in the dimers afforded terminal alkenes and dienes.
- Wlassics, Ivan,Tortelli, Vito
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scheme or table
p. 1719 - 1728
(2009/06/05)
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- PROCESS FOR THE SYNTHESIS AND SEPARATION OF HYDROFLUOROOLEFINS
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A process for the synthesis of fluorinated olefins of the formula CF3CF=CHX, wherein X is F or H comprising contacting hexafluoropropene with hydrogen chloride in the vapor phase, in the presence of a catalyst, at a temperature in the range from about 200 °C to about 350 °C, wherein the mole ratio of hydrogen chloride to hexafluoropropene is from about 2:1 to about 4:1, separating the 1-chloro-1,2,3,3,3-pentafluoro-1-propene, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene and hydrogen fluoride products from unreacted hexafluoropropene, and hydrogen chloride by distillation, hydrogenating either the 1-chloro-1,2,3,3,3-pentafluoro-1-propene, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene or mixture thereof over a catalyst, and dehydrochlorinating the said hydrogenation product to produce either 1225ye or 1234yf.
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Page/Page column 12-14
(2008/12/07)
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- Reactions of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone with various amines
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The reaction of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone, perfluoroethyl perfluoroisopropyl, or bis-perfluoroisopropyl ketone with various amines has been studied and the products identified. A comparison of the reactivity of the ketones with different amines is made and identified by mass spectroscopy. The reaction of diethyl amine with all three ketones leads to two unexpected products and the mechanism of their formation is considered.
- Howell, Jon L.,Friesen, Chadron M.,Laugesen, Krista L.,van der Ende, Alice E.
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p. 178 - 184
(2008/09/17)
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- PROCESS
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The invention relates to a process for preparing a C3-6 hydrofluoroalkene comprising dehydrohalogenating a C3-6 hydrohalofluoroalkane in the presence of a zinc/chromia catalyst.
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Page/Page column 33-36
(2008/06/13)
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- SELECTIVELY REACTING OLEFINS HAVING A TERMINAL CF2 GROUP IN A MIXTURE
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A process is disclosed for reducing the mole ratio of (1) compounds of the formula Y1Y2C=CF2 wherein Y1 and Y2 are each independently H, F, CI, Br, C1-C6 alkyl or C1-C6 haloalkyl containing no more than 3 chlorine substituents, 2 bromine substituents and 1 iodo substituent to (2) saturated compounds of the formula CdHeFfCIgBrhIk wherein d is an integer from 1 to 10, and e+f+g+h+k is equal to 2d+2, provided that g is 0, 1, 2 or 3, h is 0, 1 or 2 and k is 0 or 1 and/or unsaturated compounds of the formula Y3Y4C=CY5Y6, wherein Y3, Y5 and Y6 are each independently H, F, CI Br, C1-C6 alkyl or C1-C6 haloalkyl containing no more than 3 chlorine substituents, 2 bromine substituents and 1 iodo substituent, provided that Y5 and Y6 are not both F, and Y4 is C1-C6 alkyl or C1-C6 haloalkyl containing no more than 3 chlorine substituents, 2 bromine substituents and 1 iodo substituent, in a mixture. The process involves contacting the mixture with at least one selective removal agent selected from the group consisting of SO3 and RSO3H, wherein R is selected from the group consisting of F, CI, OH, C1-C8 alkyl, C1-C8 fluoroalkyl, and C1-C8 fluoroalkoxyalkyl containing no more than two ether oxygens to selectively react the formula Y1Y2C=CF2 compounds.
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- Noncatalytic manufacture of 1,1,3,3,3-pentafluoropropene from 1,1,1,3,3,3-hexafluoropropane
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1,1,3,3,3-Pentafluoropropene (CF3CH═CF2, HFC-1225zc) can be produced by pyrolyzing 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa) in the absence of dehydrofluorination catalyst at temperatures of from about 700° C. to about 1000° C. and total pressures of about atmosphere pressure in an empty, tubular reactor, the interior surfaces of which comprise materials of construction resistant to hydrogen fluoride.
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Page/Page column 4
(2008/06/13)
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- PROCESS FOR THE PREPARATION OF 1,1,1,3,3,3-HEXAFLUOROPROPANE AND AT LEAST ONE OF 1,1,1,2,3,3-HEXAFLUOROPROPANE AND 1,1,1,2,3,3,3-HEPTAFLUOROPROPANE
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A process is disclosed for the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and at least one 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process involves (a) reacting HF, Cl2, and at least one halopropene of the formula CX3CCl=CX2 (where each X is independently F or Cl) to produce a product including both CF3CCl2CF3 and CF3CClFCClF2; (b) reacting CF3CCl2CF3 and CF3CClFCClF2 produced in (a) with hydrogen to produce a product comprising CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3, and CF3CHFCF3; and (c) recovering from the product produced in (b), CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3 and CF3CHFCF3. In (a), the CF3CCl2CF3 and CF3CClFCClF2 are produced in the presence of a chlorofluorination catalyst including a ZnCr2O4/crystalline α-chromium oxide composition, a ZnCr2O4/crystalline α-chromium oxide composition which has been treated with a fluorinating agent, a zinc halide/α-chromium oxide composition and/or a zinc halide/α-chromium oxide composition which has been treated with a fluorinating agent.
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Page/Page column 16; 19
(2008/06/13)
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- Systems and methods for producing fluorocarbons
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Systems and methods for producing fluorocarbons are provided that include contacting a saturated halogenated fluorocarbon with hydrogen and catalyst to produce a saturated hydrofluorocarbon and an unsaturated fluorocarbon. Aspects of the present invention describe systems and methods for contacting saturated halogenated fluorocarbons such as CF3CClFCF3 and/or CF3CCl2CF3 with hydrogen and catalyst. Systems and methods of the present invention also describe contacting saturated halogenated fluorocarbons with catalysts having one or more of K, Zr, Na, Ni, Cu, Ni, Zn, Fe, Mn, Co, Ti, and Pd. Aspects of the present invention also describe contacting saturated halogenated fluorocarbons with hydrogen under pressure. Saturated hydroflourocarbons and unsaturated fluorocarbons produced in accordance with the systems and methods of the present invention can include one or more of CF3CFHCF3, CF3CH2CF3, CF3CHClCF3, CF3CF═CF2, CF3CH═CF2, and CF3CCl═CF2.
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Page/Page column 3-14
(2008/06/13)
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- Method of making fluorinated propanes
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The invention provides a process for the manufacture of fluoropropanes, and more particularly, the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process utilizes 3-carbon by-products, i.e. waste material, from other commercial processes as raw material. The process also avoids the use of hexafluoropropane (HFP) as a reactant for making HFC-227ea, and is able to convert any three-carbon hydrocarbon (HC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC) compound or any halogenated propanes and produce high valued three-carbon hydrofluorocarbons (HFCs) at significantly lower cost than current commercial processes.
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- Processes for the purification and use of 2-chloro-1,1,1,2,3,3,3-heptafluoropropane and zeotropes thereof with HF
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A process is disclosed for the separation of a mixture of HF and CF3CClFCF3. The process involves placing the mixture in a separation zone at a temperature of from about ?30° C. to about 100° C. and at a pressure sufficient to maintain the mixture in the liquid phase, whereby an organic-enriched phase comprising less than 50 mole percent HF is formed as the bottom layer and an HF-enriched phase comprising more than 90 mole percent HF is formed as the top layer. The organic-enriched phase can be withdrawn from the bottom of the separation zone and subjected to distillation in a distillation column to recover essentially pure CF3CClFCF3. The distillate comprising HF and CF3CClFCF3can be removed from the top of the distillation column while essentially pure CF3CClFCF3can be recovered from the bottom of the distillation column. The HF-enriched phase can be withdrawn from the top of the separation zone and subjected to distillation in a distillation column. The distillate comprising HF and CF3CClFCF3can be removed from the top of the distillation column while essentially pure HF can be recovered from the bottom of the distillation column. If desired, the two distillates can be recycled to the separation zone. Also disclosed are compositions of hydrogen fluoride in combination with an effective amount of CF3CClFCF3to form an azeotrope or azeotrope-like composition with hydrogen fluoride. Included are compositions containing from about 38.4 to 47.9 mole percent CF3CClFCF3. Also disclosed are processes for producing 1,1,1,2,3,3,3-heptafluoro-propane. One process uses a mixture comprising HF and CF3CClFCF3and is characterized by preparing essentially pure CF3CClFCF3as indicated above, and reacting the CF3CClFCF3with hydrogen. Another process uses an azeotropic composition as described above, and reacts the CF3CClFCF3with hydrogen in the presence of HF. Also disclosed is a process for producing hexafluoropropene. This process is characterized by preparing essentially pure CF3CClFCF3as indicated above, and dehalogenating the CF3CClFCF3.
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Page column 7-8
(2008/06/13)
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- Preparation of 1-X-2,2-Difluoroethenylxenon(II) Tetrafluoroborates [CF 2=CXXe][BF4]
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The new type of alkenylxenon(II) salts [CF2=CXXe] [BF 4] (X = H, Cl, CF3) was prepared by reacting the corresponding alkenyldifluoroboranes CF2=CXBF2 with XeF2 in 1,1,1,3,3-pentafluoropropa
- Frohn, Hermann-Josef,Bardin, Vadim V.
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p. 2465 - 2469
(2008/10/09)
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- Synthesis of Hexafluoroacetone by Catalytic Oxidation of Hexafluoropropylene
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Oxidation of hexafluoropropylene with molecular oxygen in a fixed bed of a catalyst (activated carbon promoted with alkali metal fluorides) was studied.
- Igumnov,Lekontseva,Shipigusev,Gomzyakova,Soshin
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p. 170 - 171
(2007/10/03)
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- Electrophilic, catalytic alkylation of polyfluoroolefins by some fluoroalkanes
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New data are presented on the antimony pentafluoride catalyzed reaction of hydrofluorocarbons such as CH3F, CH2F2, CH3CHF2 and RfCH2CH2F with fluoroolefins. The condensation of CH2F2 and fluoroolefins CF2=CFX (X=F, CF3) proceeds under mild conditions producing the corresponding propanes FCH2CFXCF3 in moderate to high yield. Under similar conditions methyl fluoride reacts with tetrafluoroethylene giving CH3CF2CF3. However, a complex mixture of products forms in the analogous reaction with hexafluoropropene. The structures of the products of the reactions of CH3CHF2 and tetrafluoroethylene and F-butylethylene were determined.
- Belen'Kii,Petrov,Resnick
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- EPR studies of anion-radicals formed by reduction of perfluorinated α-triketones with some metals of groups I-III
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Reaction of α,β-bis-fluorosulfatoketones i-C3F7(CFOSO2F)2C(O)RF, (RF=C2F5, i-C3F7) with AcONa/AcOH afforded perfluoro-α-triketones i-C3/sub
- Shaposhnikova,Sterlin,Solodovnikov,Bubnov,Tumanskii
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- An unusual reaction of hexafluoroacetone with methylenediphosphanes: Facile synthesis of carbodiphosphoranes
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The oxidation of the methylenediphosphanes 3a,b with hexafluoroacetone does not lead to the expected dioxaphospholane heterocycles, but yields quantitatively the carbodiphosphoranes 5a,b. Compounds 5a,b easily add HCl, HF or Cl2 to the ylidic bonds. The chloro derivative 14b, and its analogue 17 were used for the synthesis of phosphonium substituted carbenes.
- Shevchenko, Igor,Mikolenko, Rostislav,Loss, Sandra,Gruetzmacher, Hansjoerg
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p. 1665 - 1671
(2007/10/03)
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- Transformations of F-Alkyl Iodides and Bromides Induced by Nickel(0) Carbonyl
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Adducts of primary F-alkyl iodides with nickel carbonyl are formed readily in donor solvents and pyrolyze at 100-150 °C to give olefinic coupling products in high yield. The mechanism proposed to account for the observed chemistry involves preferential α-elimination of fluorine with formation of a carbenoid species complex coordinated to nickel. Differences in reaction paths among several types of substrate halides are rationalized on the basis of polarization of the Ni-C bond in the adducts. Support for these proposals is provided by state-of-the-art calculations.
- Krespan, Carl G.,Dixon, David A.
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- The reactivities of perfluoroisopropyl and tert-butyl radicals towards hydrogen atom abstraction from triethylsilane
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The rates of hydrogen abstraction from triethylsilane by the highly electrophilic perfluoroisopropyl and perfluoro-tert-butyl radicals have been obtained through competition experiments. These rates, 3.6 × 106 and 2.4 × 108 M-1 s-1, respectively, are indicative of substantial reactivity enhancements, relative to perfluoro-n-alkyl radicals, derived from their enhanced electrophilicity and, in the latter case, from a much stronger forming C-H bond.
- Dolbier Jr., William R.,Li, An-Rong
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- Thermal decomposition of branched-chain perfluoroalkanes
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The pyrolysis of some branched perfluoroalkanes has been studied.Homolytic cleavage of the most hindered carbon-carbon bond occurs, followed by coupling and rearrangement of the radicals so formed.This mechanism accounts for all the reaction products.Some kinetic and thermodynamic data are presented.
- Tortelli, V.,Tonelli, C.,Corvaja, C.
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p. 165 - 174
(2007/10/02)
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- REACTION OF ORGANIC COMPOUNDS WITH SF4-HF-HALOGENATING SYSTEM VII. REACTIONS OF OLEFINS WITH THE SF4-HF-Cl2(Br2) SYSTEM
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Under the influence of the SF4-HF-Cl2(Br2) system halogen-containing olefins undergo conjugate halogenofluorination.It was shown for the case of (Z)- and (E)- 1,2-dichloroethenes that these reactions take place anti-stereospecifically through the formation of the bromonium ions.The accumulation of chlorine atoms in the olefin molecule hinders electrophilic addition of stoichiometric equivalents of ClF and BrF at the double bond.The SF4-HF-Br2 system is an effective agent for substitutive fluorination of organic compounds containing bromine.Only the bromine atoms situated at the secondary carbon atom are substituted by fluorine.
- Kunshenko, B. V.,Mokhamed, Nagib Mukhtar,Omarov, V. O.,Muratov, N. N.,Yagupol'skii, L. M.
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p. 511 - 518
(2007/10/02)
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- Perfluoroisopropylcadmium and copper: preparation, stability and reactivity
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Perfluoroisopropylcadmium can be prepared in excellent yield (98percent) from (CF3)2CFI and activated cadmium powder in DMF at room temperature under degassed conditions.The resultant cadmium reagent undergoes metathesis with copper(I) salts to give perfluoroisopropylcopper, in quantitative yield.While perfluoroisopropylcopper is stable in DMF at room temperature under nitrogen, the cadmium counterpart decomposes to a mixture of dimers and trimers of hexafluoropropene, under the same conditions.Sulfur dioxide can be inserted into the cadmium-carbon bond in perfluoroisopropylcadmium while no reaction was observed with corresponding copper reagent.No stable F-alkylcadmium could be obtained from the raction of CF3CF2CFICF3 with either Cd powder or Me2Cd; only the elimination product, CF3CF=CFCF3, was observed.Perfluoroalkylation reactions with F-isopropylcadmium/copper in DMF met with limited success.
- Nair, Haridasan K.,Burton, Donald J.
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p. 341 - 351
(2007/10/02)
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- Condensation du chloroforme avec des olefins fluorees en milieu basique
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The condensation of CHCl3 with CF3CF=CF2 under phase-transfer catalysis leads mainly to CF3CFH-CF=CCl2 (1a).In the case of CF2=CFCl, a cyclopropane adduct 3b is obtained along with CHClF-CF=CCl2 (1b).The yields of adducts 1a,b or 3b are ca. 30percent.As the working conditions are simple and the starting materials are readily available, the method could provide an interesting route to some perhalogeno-cyclopropanes and short-chain hydro-halogeno alkenes.
- Nguyen, Thoai,Wakselman, Claude
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p. 241 - 248
(2007/10/02)
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- PERFLUORINATED INTERNAL α-OXIDES IN REACTION WITH SODIUM METHOXIDE
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Perfluorinated internal α-oxides interact with sodium methoxide in methanol, giving the products from "haloform" dissociation of the intermediately formed α-methoxy-perfluoro ketones.In unsymmetrical disubstituted perfluorinated internal α-oxides nucleophilic attack by the methoxide ion is directed at both carbon atoms of the epoxide ring, while the trisubstituted perfluorinated α-oxides from the products from regiospecyfic opening of the ring.The stability of the α-oxides to the action of sodium methoxide increases with increase in the size of the perfluoroalkyl substituents in the epoxide ring.
- Zapevalov, A. Ya.,Filyakova, T. I.,Peschanskii, N. V.,Kodess, M. I.,Kolenko, I. P.
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p. 441 - 445
(2007/10/02)
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- BROMINATION OF FLUOROALKENES PART 5.-KINETICS OF FORWARD AND REVERSE REACTIONS IN THE SYSTEM Br2+i-C3F7HHBr+i-C3F7Br
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The kinetics of the forward and reverse reactions in the gas-phase system have been studied.The slow steps for the forward and reverse reactions, respectively, are .The Arrhenius parameters obtained, for the range 421-534 deg C, are .The competitive brominations of mixtures of i-C3F7H+C2F5H and i-C3F7H+n-C3F7H have been studied over the ranges 249-430 and 220-402 deg C, respectively.Each system yielded Arrhenius parameters for reaction (2) which are in excellent agreement with those given above.The results lead to the following bond dissociation energies at 298 K: Attempts were made to measure D using competitive photobromination and photochlorination.However, (CF3)3C-H is so unreactive that only the approximate result D ca. 456 kJ mol-1 was obtained.The trends in C-H and C-Br bond dissociation energies are compared in alkanes, fluoroalkanes and the corresponding bromides.
- Evans, Brian S.,Weeks, Ian,Whittle, Eric
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p. 1471 - 1482
(2007/10/02)
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- SYNTHESIS AND REACTIONS OF OXYGEN-CONTAINING ORGANOFLUORINE COMPOUNDS. VII. REDUCTION OF PERFLUORINATED DICARBONYL COMPOUNDS.
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The reduction of perfluorinated α,ω-diisopropyl diketones with lihium aluminium hydride in aprotic solvents led to the production of secondary diols.For the case of perfluoro-(2,9-dimethyl-3,8-decanedione) and perfluoro-(7-methyl-6-ketooctanoyl)fluoride it was shown that selective reduction of the carbonyl groups is possible, depending on the reaction conditions and on the nature of the metal hydride complex.
- Saloutina, L. V.,Zapevalov, A. Ya.,Kodess, M. I.,Kolenko, I. P.
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p. 685 - 689
(2007/10/02)
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- Process for the manufacture of octafluoropropane
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Octafluoropropane, C3 F8, is prepared by a two-step process. In the first step hexafluoropropene is reacted with hydrogen fluoride in the presence of a chromium oxyfluoride catalyst. The 2H-heptafluoropropane obtained is reacted with fluorine in the presence of a catalyst which contains a subgroup element of the Periodic System as a free metal or as a fluoride. Octafluoropropane is isolated from the resulting gas mixture. Hydrogen fluoride also obtained may be recycled to the first reaction step.
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- Inorganic chemistry of fluorocarbenes. 1. Reactions of tetrafluoroethylidene with fluorine-containing phosphines
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The interactions of tetrafluoroethylidene with three fluorine-containing phosphines have been investigated. The source of the carbene is the pyrolytic decomposition of C2F5SiF3 at 200°C. The reaction of CF3CF with PF3 generates CF2=CFPF4 and PF5; reaction with (CF3)3P leads to (CF3)2PCF(CF3)2; and reaction with (CF3)2PCF(CF3)2 produces the fluorocarbon (CF3)2CFCF(CF3)2. The possibility that the vinylphosphorane product of the PF3 reaction results from fluorine-transfer rearrangement of C2F5PF2 as an intermediate product was discredited by a demonstration that C2F5PF2 is thermally stable under the reaction conditions. Other mechanistic pathways are discussed.
- Sharp, Kenneth G.,Schwager, Irving
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p. 1697 - 1701
(2007/10/13)
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