- The synthesis of perfluoroamine using nitrogen trifluoride
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The reactions of nitrogen trifluoride (1) with hexafluoropropene (2) in the presence of cesium fluoride (CsF) gave 2- (3) and 1-heptafluoropropyldifluoroamine (4) in moderate yields. Tetrafluoroethylene (6) and octafluoro-2-butene (8) similarly reacted with 1 to give corresponding products.
- Takagi, Toshiyuki,Tamura, Masanori,Shibakami, Motonari,Quan, Heng-Dao,Sekiya, Akira
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- Synthesis of perfluoroalkanes in high-temperature fluorination of graphite with fluorine in a reactor with a free-falling graphite bed
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Reaction between fluorine and graphite in a reactor with a free-falling bed of graphite was studied in relation to the temperature in the reaction zone, ratio of the feeding rates of fluorine and graphite, and dilution of fluorine with an inert gas. Pleiades Publishing, Inc., 2006.
- Shelopin,Pashkevich,Alekseev,Mukhortov,Petrov,Asovich
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- GAS PHASE RADIATION CHEMISTRY OF HEXAFLUOROETHANE
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The Co-60 gamma radiolysis of gaseous C2F6 was investigated at 50 Torr pressure, both pure and with 10percent oxygen added.For the pure system, the radiolytic products and their respective G values were CF4, 2.27; C3F8, 0.23; C4F10, 0.09; C5F12, 0.015; and C6F14, 0.009.All radiolysis products except for CF4 (C = 0.61) were eliminated when 10percent O2 was added as scavenger.The results are discussed mainly in terms of the decomposition of excited C2F6 into free radicals, which can then combine.The unscavenged CF4 is accounted for by the ion-molecule reaction CF3+ + C2F6 -> CF4 + C2F5+.
- Scanlon, Michael D.,Hanrahan, Robert J.
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- Reaction of Pentafluoroethyl Radicals with Cyanogen Chloride
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The reaction of C2F5 radicals with cyanogen chloride was studied between 293 and 573 K, using perfluoroethyl iodide as the free-radical source. The main product, C2F5Cl is formed via an addition reaction or by abstraction of a chlorine atom by C2F5.The reactions involved are C2F5+ClCN->C2F5Cl+CN (2) C2F5+ClCN->/C2F5Cl+CN (4) C2F5+C2F5->C4F10 The Arrhenius plot shows pronounced curvature.The following rate constants were obtained for reactions (2) and (4) where kc is the rate constant for C2F5 combination. The results are compared with those for the reaction of CF3 with ClCN.
- Voehringer, Cecilia M. de,Staricco, Eduardo H.
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- Synthesis of perfluoroalkanes by high-temperature reaction of graphite with fluorine in a fluidized bed
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Synthesis of lower perfluoroalkanes (tetrafluoromethane, hexafluoroethane, octafluoropropane, decafluorobutane) by high-temperature reaction of graphite with fluorine in a fluidized bed was studied.
- Pashkevich,Shelopin,Mukhortov,Petrov,Alekseev,Asovich
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- Decomposition characteristics of C5F10O/air mixture as substitutes for SF6 to reduce global warming
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Sulfur hexafluoride (SF6) is widely used in the power industry but is a serious greenhouse gas. Many researchers committed to achieving sustainable development of the power industry are finding alternatives to SF6 gas. C5F10O performs well in terms of environmental protection, insulation, and safety and is a potential environment-friendly alternative gas. In this paper, the insulation and decomposition characteristics of C5F10O/air gas mixture were examined using gas-insulation performance test platform, and decomposition products were detected by gas chromatography–mass spectrometry. The formation mechanism and distribution of C5F10O decomposition products were analyzed through reactive molecular dynamics method and density functional theory. The influence of air on the decomposition of C5F10O was also evaluated. Results showed that the decomposition of C5F10O/air gas mixture mainly produces CF3[rad], C3F7[rad], C4F7O[rad], CO, CF2[rad], CF[rad], F[rad] and CF4. The breakdown voltage of C5F10O/air gas mixture decreased slightly after repeated breakdown tests, and CF4, C2F6, C3F8, C3F6, C4F10, CF2O were detected. These results can serve as a reference for the systematic comprehension of the decomposition characteristics of C5F10O/air gas mixture and for related engineering applications.
- Li, Yi,Zhang, Xiaoxing,Xiao, Song,Chen, Qi,Wang, Dibo
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- Preparation method for perfluoroalkane
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The invention discloses a preparation method for perfluoroalkane. The preparation method comprises the following steps: adding a fluorination reagent into a reaction vessel, stirring the fluorination reagent at room temperature, introducing fluorine-nitrogen gas mixture into the reaction vessel for activation of the fluorination reagent and continuing stirring for half an hour, wherein the concentration of fluorine gas in the fluorine-nitrogen gas mixture is 0.5 to 10%, and the molar weight of the fluorine-nitrogen gas mixture is 1 to 5% of the molar weight of the fluorination reagent; after completion of stirring, relieving residual pressure in the reaction vessel, and adding perfluoroalkyl halide and a solvent into the reaction vessel for a reaction at 150 to 200 DEG C for 5 to 10 h, wherein a mol ratio of perfluoroalkyl halide to the fluorination reagent is (1: 1) to (1: 2), and a mol ratio of perfluoroalkyl halide to the solvent is (1: 5) to (1: 15); and after a reaction product is obtained upon completion of the reaction, cooling the reaction product to room temperature and distilling the reaction product to obtain perfluoroalkane. The method provided by the invention has the advantages of simple equipment, high operation security, etc.
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Paragraph 0030; 0031
(2016/11/28)
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- Investigation of CF2 carbene on the surface of activated charcoal in the synthesis of trifluoroiodomethane via vapor-phase catalytic reaction
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This paper investigates the synthetic mechanism of trifluoroiodomethane (CF3I) in the reaction of trifluoromethane and iodine via vapor-phase catalytic reaction. It is suggested that CF2 carbene is the key intermediate and is formed in the pyrolysis process of CHF3 at high temperature. However, in pyrolysis of CHF3 under activated charcoal (AC) existing conditions, no C2F4 was detected. H2 and 2-methyl-2-butene could not trap the CF2 carbene. When treating the remained compounds on the used AC with H2, CH4 is formed on the process. It is proposed that CF2 carbene combines with AC strongly and transfers into CF3 radical on heat. In addition, it is found that the AC is not only the catalyst supporter to form CF3I, but also a co-catalyst to promote the formation of CF2 carbene and CF3 radical.
- Yang, Guang-Cheng,Lei, Shi,Pan, Ren-Ming,Quan, Heng-Dao
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experimental part
p. 231 - 235
(2009/08/07)
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- Amine-induced decomposition of perfluoroalkanesulfonyl fluorides
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Perfluoroalkanesulfonyl fluorides (CnF2n+1SO 2F) decompose slowly even at -20°C in the presence of tertiary heteroaromatic or aliphatic amines to form the corresponding perfluorinated alkanes (CnF2n+2
- Bennua-Skalmowski, Baerbel,Klar, Ulrich,Vorbrueggen, Helmut
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p. 1175 - 1178
(2008/12/22)
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- Carbon-chain isomerization during the electrochemical fluorination in anhydrous hydrogen fluoride - A mechanistic study
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The compounds i-C4H9SO2F, i-C3H7SO2F and cyclo-C3 H7C(O)F have been subjected to electrochemical fluorination in anhydrous hydrogen fluoride. The resulting products were fully analyzed by NMR spectroscopy. From the reaction balances, literature data and quantum chemical calculations, a new mechanism for carbon-chain isomerization during the electrochemical fluorination (ECF) is proposed. The key step in the formation of isomeric products is believed to be a ring closure reaction involving carbo-cationic or biradical intermediates.
- Ignat'ev, Nikolai V.,Welz-Biermann, Urs,Heider, Udo,Kucheryna, Andriy,von Ahsen, Stefan,Habel, Wolfgang,Sartori, Peter,Willner, Helge
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- Electrochemical fluorination of unsaturated sulfides and sulfones
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Electrochemical fluorination of some unsaturated sulfides and sulfones and their reactions with anhydrous HF were studied.
- Grigor'eva,Shainyan,Kaurova,Gracheva,Lesnevskaya,Barabanov
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p. 1095 - 1100
(2007/10/03)
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- Improvements in or relating to contrast agents
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Combined preparations comprising an injectable gas dispersion and a coadministrable diffusible component which is capable of inward diffusion into the dispersed gas so as to promote temporary growth of the gas in vivo, the preparations being for use as contrast agents in ultrasound cardiac studies of patients who have undergone physical exercise-induced stress in order to promote vasodilatation.
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- Electrochemical fluorination of hexahydroazepine, methylpiperidines and methyl 1-hexahydroazepine-acetate: The preparation of F-(1-hexahydroazepine-acetyl fluoride) and its derivatives
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The electrochemical fluorination of hexahydroazepine (1), methylpiperidines (2) [2-methylpiperidine (2a), 3-methylpiperidine (2b), 4-methylpiperidine (2c)] and methyl 1-hexahydroazepine-acetate (3) was examined. An extensive cleavage of the C-N bond occurred in the fluorination of secondary cyclic amines (1, 2a-c) resulting in only a small yield of the corresponding F-(N-fluoro cyclic amines). F-(1-hexahydroazepine-acetyl fluoride) (4) was obtained in a fair yield from the fluorination of 3 along with F-[(methylpiperidino)-acetylfluoride] which was formed as a result of the isomerization of 3 during fluorination. In addition, several derivatives of 4 were synthesized. F-(1-iodomethyl-hexahydroazepine) (4a) was prepared by the reaction of 4 with anhydrous LiI. The compound 4 was converted into its potassium salt (4c) via methyl F-(1-hexahydroazepine-acetate) (4b), which upon pyrolysis in the presence or absence of ethylene glycol resulted in the formation of 1-difluoromethyl-dodecafluoro(hexahydroazepine) (4d) and F-(3,4,5,6-tetrahydroazepine) (4e), respectively. F-(1-hexahydroazepine-acetoamide) (4f), F-(1-hexahydroazepine-acetonitrile) (4g) and corresponding p-methoxyanilide (4h) were also derived from 4.
- Abe, Takashi,Pandey, Sushil K.,Baba, Hajime
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p. 149 - 157
(2007/10/03)
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- Electrochemical fluorination of aliphatic secondary amines
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Electrochemical fluorination (ECF) has been examined for six aliphatic secondary amines: N,N-di-ethylamine, N-ethyl,N-n-propylamine, N,N-di-n-propylamine, N-ethyl,N-iso-propylamine, N,N-di-iso-propylamine, and N-methyl,N-n-butylamine. It was found from these amines that not only the corresponding F-(N-fluoro-N,N-dialkylamines) but also F-imines having the same number of the carbon atoms were formed in low yields. The suppression of the C-N bond cleavage (blocking effect) which is expected to occur during fluorination due to the presence of bulky N-alkyl group was not observed as a result of the ECF of these aliphatic secondary amines. It was also found that the change of the initial solute concentration of N,N-di-n-propylamine did not affect on the product yields, which is usually observed for cyclic secondary amines. Several F-(N-fluoro-N,N-dialkylamines) were treated with triphenylphosphine for conversion into the corresponding F-imines. An imine bond was generated during this defluorination exclusively at the site of the alkyl group with a longer chain length when there were two different alkyl groups present in F-(N-fluoro-dialkylamines).
- Abe, Takashi,Hayashi, Eiji,Baba, Hajime
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- Technology for the preparation of perfluoro-organic compounds
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Fluorination by elemental fluorine of fluorine-containing alkenes, alkanes, ethers and tertiary amines was investigated, aimed at obtaining the perfluorinated analogs. The factors affecting yield of the target compounds were studied. Elements of technology were elucidated.
- Moldavskii, Dmitrii D.,Bispen, Tatjana A.,Kaurova, Galina I.,Furin, Georgii G.
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p. 157 - 167
(2007/10/03)
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- Electrochemical fluorination of (N,N-dialkylamino)alcohols
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Series of amino alcohols including 2-(N,N-dialkylamino)ethanols, 3-(N,N-dimethylamino)propanol and 4-(N,N-dimethylamino)butanol were subjected to electrochemical fluorination. In the case of 2-(N,N-dialkylamino)ethanols, the F-(2-N,N-dialkylamino)acetyl fluorides were obtained in fair to good yields. Yields of each target compound were strongly dependent on the kind of the dialkylamino group. Cyclic amines having an N-(2-hydroxylethyl) group afforded the corresponding F-[N-(c-alkylamino)-substituted acetyl fluorides]. Their yields were generally better than those of acyclic analogs. Several 2-(N,N-dialkylamino)ethanols and 3-(N,N-dimethylamino)propanol were converted into the corresponding trimethylsilylethers, aminoalkyl methyl carbonates and bis-aminoalkyl carbonate, respectively, and they were subjected to fluorination for a comparison of the yield with that obtained from that of the parent aminoalcohol.
- Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Ono, Taizo,Nishida, Masakazu,Soloshonok, Irina,Okuhara, Kunio
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p. 229 - 237
(2007/10/03)
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- The dark reactions F2 + CF3I, C2F5I, and n-C3F7I
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The reactions between F2 and the lowest members of the homologous series of perfluoroalkyl iodides (CF3I, C2F5I, and n-C3F7I) have been studied. For these compounds, an exponential decrease
- Johnson,Walters,Dorko
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- DIRECT GAS-PHASE CATALYTIC FLUORINATION OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS
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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.
- Zakharov, V. Yu.,Denisov, A. K.,Novikova, M. D.
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p. 1942 - 1945
(2007/10/03)
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- The electrochemical fluorination of N-containing carboxylic acids (Part 4). Fluorination of methyl 3-dialkylamino-isobutyrates and methyl 3-dialkylamino-n-butyrates
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Several methyl esters of 3-dialkylamino-substituted n- and isobutyric acids have been subjected to electrochemical fluorination to give the corresponding perfluoroacid fluorides.Dimethyl, diethyl, pyrrolidino, morpholino, piperidino and N-methylpiperazino groups were investigated as dialkylamino substituents.The structure/yield relationship was evaluated both in terms of the structure of the acid and the kind of amino group, respectively.Better yields of perfluoroacid fluorides were obtained from methyl esters having isobutyric acid skeletons than those having n-butyric acid groups, and from the acids containing cyclic amino groups than those containing acyclic ones.
- Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Hayakawa, Yoshio,Nishida, Masakazu,Baba, Hajime
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p. 193 - 202
(2007/10/02)
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- Fluorinated poly(ether sulfones)
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Polymers comprising fluorine-containing poly(ether sulfones) and monomers comprising aromatic fluorine-containing sulfones used in the preparation of these polymers.
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- The electrochemical fluorination of nitrogen-containing carboxylic acids. Fluorination of methyl esters of 3-dialkylamino propionic acids
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Six methyl esters of 3-dialkylamino-substituted propionic acids were subjected to electrochemical fluorination to give the corresponding perfluoroacid fluorides.The following dialkylamino substituents were investigated: diethylamino, di-n-propylamino, di-n-butylamino, pyrrolidino, morpholino and piperidino groups.These perfluoroacid fluorides, which were obtained in fair yields, are considered to be prospective key precursors for preparing soft-type (degradable) fluorochemicals.The salts show a considerable lowering of surface tension in aqueous solution.Thephysical properties of all the perfluoroacid fluorides obtained are reported, together with their spectroscopic data (19F NMR, mass and IR spectra).
- Abe, Takashi,Hayashi, Eiji,Fukaya, Haruhiko,Hayakawa, Yoshio,Baba, Hajime,et al.
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p. 101 - 111
(2007/10/02)
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- THE ELECTROCHEMICAL FLUORINATION OF NITROGEN-CONTAINING CARBOXYLIC ACIDS. FLUORINATION OF METHYL ESTERS OF CYCLIC AMINOGROUP SUBSTITUTED CARBOXYLIC ACIDS
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Nine methyl esters of cyclic amino-group substituted carboxylic acids related to glycine, alanine or β-alanine were subjected to electrochemical fluorination.This afforded the corresponding perfluoroacid fluorides together with cleavage products in fair yields.As cyclic amino-substituents, pyrrolidino-, morpholino-, piperidino-, hexamethyleneimino- and N'-methylpiperazinyl-groups were investigated.The formation of cyclized by-products was not observed, which contrasts with the fluorination of aliphatic dialkylamino-substituted carboxylic acids.From such methyl 2-cyclic amino-propionates (cyclic amino-group: a pyrrolidino, a morpholino or a piperidino-group), the perfluorinated methyl esters were obtained together with the corresponding perfluoroacid fluorides in yields of 1-2percent and 14-29percent, respectively.The formation of the former compounds is ascribed to the blocking effect of the bulky cyclic amino-groups.The physical properties of the new compounds obtained are reported together with their spectral (19F NMR, Mass and IR) data.
- Abe, Takashi,Hayashi, Eiji,Fukaya, Haruhiko,Baba, Hajime
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p. 173 - 196
(2007/10/02)
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- CURRENT BALANCE OF THE ELECTROCHEMICAL FLUORINATION OF A TRIALKYLAMINE
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The electrochemical fluorination of dibutylmethylamine was studied.All the fluorination products formed, liquid, gaseous, and dissolved in HF, and also the hydrogen evolved were quantitatively determined.From either their formulae or their relative fluorine contents the amount of current necessary for their formation was estimated.Altogether, the fluorination products determined cover about 86-97 percent of the current applied.A major part of the current was consumed by production of polyfluorinated products, which remained dissolved in the hydrogen fluoride.
- Dimitrov, A.,Stewig, H.,Ruediger, St.,Kolditz, L.
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- Synthesis of new perfluorotertiary amines containing geminal pentafluorosulfanyl, SF5, groups
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The perfluorinated tertiary amines (SF5)2NCF3 [1], (SF5)2NC2F5, and (SF5)2NC3F7 have been prepared by the following scheme. Their overall yields were found to decrease markedly with respect to increases in the length of the perfluoro- {A figure is presented} alkyl chain. In fact, attempts to prepare (SF5)2NC4F9 have been unsuccessful thus far. The N-chloroamines were also reacted with simple olefins to give a variety of addition products such as SF5N(CF3)CH2CH2Cl, SF5N(CF3)CF2CF2Cl, SF5N(C2F5)CH2CH2Cl, and SF5N(C4F9)CH2CH2Cl.
- Nielsen, Jon B.,Thrasher, Joseph S.
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p. 407 - 420
(2007/10/02)
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- THE FLUORINATION OF BUTANE OVER COBALT TRIFLUORIDE
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The fluorination of butane over cobalt trifluoride has given a complex mixture of partially fluorinated compounds: 51 of these have been identified, comprising over 99percent of the products.Most were polyfluor-butanes but 1-2percent were polyfluoro-2-methylpropanes.The reaction has no synthetic utility.There was some selectivity in the fluorination: secondary C-H was convertart byed into C-F more easily then primary, and the ease of replacement of a particular H was reduced by geminal vicinal fluorines.A computer model of the fluorination was only partially successful, perhaps because the fluorination proceeded in part by simple F for H replacement and in part via alkenes: the model only allowed for the former.
- Burdon, James,Ezmirly, Saleh T.,Huckerby, Thomas N.
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p. 283 - 318
(2007/10/02)
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- The infrared multiphoton dissociation of hexafluoroethane
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The infrared multiphoton dissociation (IRMPD) of "neat" hexafluoroethane has been investigated for the first time.The stable products of photolysis are CF4, C2F4, C3F8, and C4F10.Product analysis involved tunable diode laser (TDL) and fourier transform infrared spectroscopy, as well as gas chromatography where applicable.The high sensitivity and resolution of the TDL allows for measurement of the stable products CF4 and C2F4 after irradiation by a single infrared laser pulse.The yield of CF3 radicals produced by the IRMPD of C2F6 as a function of fluence was measured via the TDL high frequency modulation technique.The role of added H2, leading to elimination of CF4 and increase of C2F4 as products, is clarified.
- Brown, Carl E.,Smith, Donald R.
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p. 609 - 614
(2007/10/02)
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- FREE RADICAL CHEMISTRY, PART 5. A NEW APPROACH TO THE SYNTHESIS OF PERFLUORINATED ETHERS
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Fluorinations of the free-radical adducts of fluorinated alkenes, to ethers, over cobalt trifluoride are described and perfluorinated ethers are obtained at temperatures in excess of 400 deg C.The effect of structure on the formation of perfluoroethers is outlined.
- Chambers, Richard D.,Grievson, Brian,Drakesmith, Frederick G.,Powell, Richard L.
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p. 323 - 340
(2007/10/02)
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- Aerosol Direct Fluorination: Alkyl Halides. 2. Chlorine Shift and the Stability of Radicals
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Unlike alkyl bromides and iodides, alkyl chlorides are shown to be stable to direct fluorination, even under ultraviolett irradiation, at temperatures of 30 deg C and below.Although less reactive than the bromides and iodides, F-alkyl chlorides may be derivatized, presenting another example of direct fluorination-survivable functionality.High (63 percent) to moderate (32 percent) isolated yields of the analogous perfluororalkyl chlorides can be synthesized by aerosol direct fluorination of 1-chloropropane, 1-chlorobutane, 1-chloro-2-methylpropane, 1-chloro-3-methylbutane, 1-chlo-ro-2-methylbutane, and chlorocyclopentane with generally less than 20 percent C-C bond cleavage.Tertiary alkyl chlorides generally undergo intramolecular 1,2-chloride shift in the earliest stages of reaction in a manner characteristic of β-chloro radicals forming principally primary F-alkyl chlorides.Thus 2-chloro-2-methylpropane produces 1-chloro-F-2-methylpropane (47 percent), and 2-chloro-2-methylbutane produces a 16:6.3:1 ratio of 1-chloro-F-2-methylbutane, 1-chloro-F-3-methylbutane, and 2-chloro-F-3-methylbutane, respectively, in 32 percent combined yield.Secondary alkyl chlorides undergo a similar but incomplete rearrangement producing mixtures of primary and secondary F-alkyl chlorides.Thus 2-chloropropane produces a 2:1 mixture of 2-chloro-F-propane and 1-chloro-F-propane in 50 percent combined yield; 2-chlorobutane produces a 1:1.5 mixture of 2-chloro-F-butane and 1-chloro-F-butane in 34 percent combined yield, and 3-chloropentane produces a 2:3:1 mixture of 3-chloro-F-pentane, 2-chloro-F-pentane, and 1-chloro-F-pentane, respectively, in a combined yield of 30 percent.Because secondary alkyl chlorides partially rearrange but primary alkyl chlorides donot rearrange at all on fluorination, doubt is cast on the postulate that the intermediate radicals are equilibrating.
- Adcock, James L.,Evans, William D.
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p. 2719 - 2723
(2007/10/02)
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- ELECTROCHEMICAL FLUORINATION OF N-CHLOROALKYL-SUBSTITUTED CYCLIC AMINES
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The electrochemical fluorination of such N-chloroalkyl substituted cyclic amines as N-chloromethylpyrrolidine (1), N-(3-chloropropyl)pyrrolidine (2), N-chloromethylpiperidine (3), N-(2-chloroethyl)piperidine (4), N-(3-chloropropyl)piperidine (5), N-chloromethylmorpholine (6), N-(3-chloropropyl)morpholine (7), N-(2-chloroallyl)morpholine (8) has been conducted.Except in the cases of the N-chloromethyl-substituted ones (1,3 and 6), the corresponding chlorine-retaining-perfluoroamines were obteined in a yield of 5 - 20 percent together with perfluorinated ones (Yield = 20 - 60 percent).Neither chlorine-retaining amines nor perfluorinated amines, both of which having the original skeleton, was produced from fluorinations of 1, 3 and 6 in an appreciable yield.The spectroscopic data and physical properties of newly synthesized perfluoro-N-chloroalkyl-substituted cyclic amines are presented.
- Hayashi, Eiji,Abe, Takashi,Baba, Hajime,Nagase, Shunji
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p. 371 - 382
(2007/10/02)
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- Product distributions and isotopic selectivities in ir multiphoton dissociation of pentafluoroiodoethane
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Infrared multiphoton dissociation of pentafluoroiodoethane leads to a complex array of reaction products.For photolysis in the ν4 band the reaction mechanism involves C2F5-I bond cleavage followed by thermal dissociation of C2F5 radicals.For irradiation within the ν3 band at high fluence, efficient secondary photolysis of C2F5 radicals is postulated.At lower fluences the dissociation is isotopically selective leading to C4F10 enriched in carbon-13.
- Weinberg, E.,Gauthier, M.,Hackett, P. A.,Willis, C.
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p. 1307 - 1310
(2007/10/02)
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- THERMAL DECOMPOSITION OF PERFLUOROALKANOYL PEROXIDES IN HYDROCARBON SOLVENTS
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The rate constants were obtained for the thermal decomposition of trifluorocateyl, pentafluoropropionyl, and heptafluorobutyryl peroxides in isooctane and heptane.The obtained values were 1.2*1015 exp(-113,000/RT) sec-1, 3.7*1017 exp(-118,800/RT) sec-1, and 6.5*1012 exp(-92,000/RT) sec-1.The proportions of the gaseous products formed in the reactions at 50 deg C were as follows: In isooctane CF3H/CO2 = 0.71 0.01, C2F5H/CO2 = 0.65 0.05; in heptane CF3H/CO2 = 0.95 0.02, C2F5H/CO2 = 0.89 0.03, C3F7H/CO2 = 0.66 0.03.The thermal decomposition of the peroxides in heptane can be used for kinetic measurements by the method of competing reactions.
- Serov, S. I.,Zhuravlev, M. V.,Sass, V. P.,Sokolov, S. V.
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p. 1360 - 1362
(2007/10/02)
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