307-59-5Relevant academic research and scientific papers
Nonmetallic Wurtz coupling reaction of perfluorohexyl iodide
Kolotaev, Anton V.,Khachatryan, Derenik S.
, p. 2745 - 2747 (2018)
It is shown for the first time that the Wurtz reaction can be realized by the action of an organic substance (triphenylphosphine) on an alkyl halide (perfluoroalkyl iodide) without the use of metals. It was found that when trying to prepare the bis(3,3′-aminophenyl)(fluoroalkyl)phosphine oxide by four-step synthesis, in the first stage of the reaction of perfluoro-1-iodohexane with triphenylphosphine does not proceed towards the formation of an intermediate quaternary phosphonium salt. Instead, the carbon chain of perfluoroalkyl iodide dimerizes to form perfluorododecane – Wurtz reaction product. We have proposed a new pathway for homocoupling of perfluoroalkylhalides into even-numbered perfluoroalkanes.
Preparation method for perfluoroalkane
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Paragraph 0038; 0039, (2016/11/28)
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.
An improved procedure for the synthesis of perfluoroalkylacetylenes
Calleja-Rubio,Crette,Blancou
, p. 361 - 364 (2007/10/03)
A new and easy way to synthesize acetylene compounds is proposed. This synthesis is improved by including in one-pot, three reactions in a single step, with good yields. The reactants are commonly used compounds.
Reaction of Perfluoroalkyl Iodides with Lithium Salt of 5-Nitro-3-tert-butyl-1,3-tetrahydrooxazine
Galeeva,Makaeva,Zorin,Trifonova,Rakhmankulov
, p. 280 - 282 (2007/10/03)
Reaction of perfluoroalkyl iodides C6F13I and C8H17I with lithium salt of 5-nitro-3-tert-butyl-1,3-tetrahydrooxazine in DMSO at 20°C for 24 h in an argon atmosphere gives 5-nitro-5-perfluoroalkyl-3-tert-butyl-1,3-tetrahydrooxazines (yield 66-75%), 5,5′-bis(5-nitro-3-tert-butyltetrahydro-1,3-oxazinyl) (yield 3-5%), and, respectively, perfluorododecane and perfluorohexadecane. The reaction is accelerated under UV irradiation.
Solvent effects on the reaction of perfluoroalkyl iododes and α,ω-perfluoroalkyl diiodides with cadmium powder and dimethylcadmium
Nair, Haridasan K.,Burton, Donald J.
, p. 1 - 12 (2007/10/02)
Reaction of RfI (Rf=C6F13 or C8F17) with Cd powder in DMF at room temperature under N2 afforded RfCdX (X=I or Rf) in moderate (48-52percent) yield.Although no reaction was observed with Cd powder and RfI (Rf=C6F13 or C8F17) in CH3CN at room temperature, reaction at reflux gave the homocoupled products C6F13-C6F13 (67percent) and C8F17-C8F17 (61percent) respectively.No F-alkylcadmium reagent was detected by 19F NMR spectroscopy.Similarly, the reaction of I(CF2)nI (n=3, 4) with Cd powder in DMF and CH3CN was examined.In DMF at room temperature, the new dicadmium reagents ICd(CF2)nCdI and ICd(CF2)2nCdI (60-65percent combined yield) were formed.No reaction was observed with Cd powder and I(CF2)nI (n=3, 4, 6) in CH3CN at room temperature, but at reflux a mixture of higher α,ω-diiodoperfluoroalkanes, i.e.I(CF2)2nI, I(CF2)3nI, I(CF2)4nI, I(CF2)5nI, resulted.Treatment of I(CF2)nI (n=3, 4) with CdMe2 (1:2) in CH3CN afforded the new ω-iodo F-alkylcadmium reagents, 2Cd*(CH3CN), in 96percent (n=3) and 57percent (n=4) yields.Reaction of Me2Cd with either ICF2CF2I or BrCF2CF2I in CH3CN or HMPA at 0 deg C resulted in tetrafluoroethylene only.
Outer-sphere dissociative electron transfer to organic molecules: A source of radicals or carbanions? Direct and indirect electrochemistry of perfluoroalkyl bromides and iodides
Andrieux, Claude P.,Gélis, Laurence,Medebielle, Maurice,Pinson, Jean,Savéant, Jean-Michel
, p. 3509 - 3520 (2007/10/02)
As an example of the general problem posed in the title, the reduction of CF3Br, CF3I, C6F13I, and C8F17I by outer-sphere heterogeneous (glassy-carbon electrodes) and homogeneous (aromatic anion radicals) reagents is investigated, in aprotic solvents containing tetralkylammonium salts, by cyclic voltammetry and preparative-scale electrolysis. A RF. chemistry is thus triggered in all cases with the exception of CF3Br where a mixed RF./RF- chemistry is obtained by direct electrochemical reduction or by electron transfer from aromatic anion radicals having a close reduction potential. Quantitative analysis of the reduction kinetics of RFX (X = Br, I) and of RF. led to the following conclusions. RFX most likely undergoes a concerted electron-transfer-bond-breaking reduction involving a substantial overpotential (ca. 1.5 V for C-Br and 1.0 V for C-I), mainly governed by the C-X bond dissociation energy. RF. radicals are strongly stabilized by interaction with the solvent but are nevertheless easier to reduce than alkyl radicals on thermodynamical grounds, exhibiting however a high intrinsic barrier of the same order as for alkyl radicals. Unlike alkyl radicals, but similar to aryl radicals, RF. radicals are good H-atom scavengers and do not couple with aromatic anion radicals.
SOLVENT EFFECTS IN BETWEEN PERFLUOROALKYLIODIDES AND CADMIUM
Chen, Grace J.,Tamborski, Christ
, p. 123 - 140 (2007/10/02)
The interaction between perfluoroorgano iodides (RfI where Rf = F(CF3)2C(CF2CF2)3, n-C6F13, n-C8F17, F(CF3)2COCF2CF2, F(CF3)2CO(CF2CF2)4 and C2H5OC(O)(CF2CF2)2OCF2CF2) with cadmium in an acetonitrile solvent media produces primarily the coupled products (RfRf, 72-90percent yield) in addition to minor quantities of the reduction products (RfH).On the other hand ICF2CF2I and ClCF2CFClI, by a 1,2-dehalogenation reaction, from the olefins CF2=CF2 and CF2=CFCl, respectively, as the principal products.The interaction of RfI compounds with cadmium in other solvent media, e.g. diethyl ether, tetrahydrofuran (YHF)), N,N-dimethylformamide (DMF), and bis(2-methoxyethyl)ether(diglyme) were examined and found to produce a different ratio of RfRf and RfH products.
THERMAL DECOMPOSITION OF PERFLUOROALKANESULFONYL FLUORIDES: THE PYROLYSIS OF PERFLUORO-n-OCTANE-1-SULFONYL FLUORIDE
Napoli, M.,Fraccaro, C.,Scipioni, A.,Armelli, R.
, p. 377 - 386 (2007/10/02)
The preliminary data obtained from thermal decompositions of perfluoro-n-octane-1-sulfonyl fluoride in a continuous tubular-flow reactor are reported.The pyrolysis results in a radical reaction producing fluorocarbons, with high conversions and with yields depending on the experimental conditions.The reaction mixture composition also depends on the experimental conditions, so it is possible to obtain a prevalent formation of either light or heavy fluorocarbons.
REACTIVITE DES PERFLUOROIODOALCANES AVEC LES CARBONATES ET PYROCARBONATES D'ALCOYLES EN PRESENCE DE COUPLE METALLIQUE ZINC-CUIVRE
Benefice, S.,Blancou, H.,Commeyras, A.
, p. 1541 - 1544 (2007/10/02)
Perpluoroalkyl iodides RFI, in dissociating solvents, in the presence of zinc-copper couple give perfluoroorganic compounds RFZnI, which reac with alkyl carbonates and pyrocarbonates to give perfluorocarboxylic acids and perfluorocarboxylis esters of industrial interest.
