- Chemical Radical Synthesis in Gas Mixtures Induced by Infrared Multiple-Photon Dissociation
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Some experimental approaches to gas-phase radical chemical synthesis induced by the process of IR multiple-photon excitation of polyatomic molecules are considered.A comparison of laser and thermal initiation of gas-phase radical reaction is given.
- Bagratashvili, V. N.,Kuzmin, M. V.,Letokhov, V. S.
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- THERMOLYSE DES HALOGENURES DE PERFLUOROALCANESULFONYLE
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Perfluoroalkanesulfonyl chlorides FSO2Cl; RF= CF3, C2F5, C4F9>, decompose thermally to give the corresponding perfluoroalkyl chlorides with evolution of SO2.The latter retards the reaction, but it is catalysed by copper which also inhibits the SO2 effect. 2-methyl-2-nitrosopropane traps the perfluoroalkyl free radicals.In the presence of a perfluoroalkyl iodide FI; R'not equal RF>, other products, RFI and RFCl, are obtained.A free radical chain-mechanism is then suggested.On the other hand, perfluorobutanesulfonyl fluoride is very stable thermally.
- Oudrhiri-Hassani, M.,Brunel, D.,Germain, A.,Commeyras, A.
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- Preparation and properties of ZnBr(CF3)*2L - a convenient route for the preparation of CF3I
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ZnBr(CF3)*2L (L=DMF, CH3CN) can easily be prepared by the reaction of CBrF3 with elemental zinc in better than 60percent yield.The reaction of ZnBr(CF3)*2DMF with iodine monochloride in DMF solution yields pure CF3I in better than 70percent yield via an ecologically less damaging reaction pathway than the decarboxylation route using silver or mercury trifluoroacetate.
- Naumann, Dieter,Tyrra, Wieland,Kock, Birgit,Rudolph, Werner,Wilkes, Bernd
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- Preparation of trifluoroiodomethane via vapour-phase catalytic reaction between pentafluoroethane and iodine
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A new route for preparing C33I has been developed via a reaction between C2HF5 and I2. The influence of reaction temperature and active components of the catalysts on the amount of C33I was investigated. The result suggests that the selectivity of the C33I can be controlled by reaction conditions and active component of catalyst. The process for the formation of C33I and by-products is also discussed.
- Mao, Aiqin,Wang, Hua,Tan, Linhua,Nin, Xiangyang,Pan, Renming
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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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- Synthesis of Au(I) trifluoromethyl complexes. Oxidation to Au(III) and reductive elimination of halotrifluoromethanes
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Au(I) trifluoromethyl complexes [Au(CF3)L] (L = N-heterocyclic carbene (NHC), isonitrile, phosphine, P(OMe)3) and [Au2(CF3)2(-dppe)] are prepared by reaction of [Au(X)L] (X = Cl, I) or [Au2Cl2(-dppe)], respectively, with AgF and Me3SiCF3. The analogous reaction of PPN[Au(C6F5)Cl] (PPN+ = [Ph3PNPPh3]+) gives a mixture of complexes of the type PPN[Au(CF3)x(C6F5)2-x] (x = 0, 1, 2). Single crystals of the new complex PPN[Au(CF3)(C6F5)] are obtained by liquid diffusion from this mixture, and its crystal structure was determined by X-ray diffraction. Acyclic diaminocarbene complexes [Au(CF3){C(NEt2)(NHR)}] (R = tBu, 2,6-dimethylphenyl) are obtained by reaction of [Au(CF3)(CNR)] with NHEt2. Oxidation of the NHC complex [Au(CF3)(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with PhICl2, Br2, I2 or ICl affords [Au(CF3)(X)(Y)(IPr)] (X = Y = Cl, Br I; X = Cl, Y = I). The dicloro, dibromo, and chloro(iodo) complexes are stable in solution in the dark. In contrast, the diiodo complex is unstable and decomposes to [AuI(IPr)] and ICF3. Under photoirradiation, complexes [Au(CF3)(X)(Y)(IPr)] undergo reductive elimination to give YCF3 and [AuX(IPr)] (X = Y = Cl, Br; X = Cl, Y = I).
- Blaya, Mara,Bautista, Delia,Gil-Rubio, Juan,Vicente, Jos
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- PROCESSES FOR PRODUCING TRIFLUOROIODOMETHANE
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The present disclosure provides a gas-phase process for producing trifluoroiodomethane, the process comprising providing a reactant stream comprising hydrogen iodide and trifluoroacetyl halide selected from the group consisting of trifluoroacetyl chloride, trifluoroacetyl fluoride, trifluoroacetyl bromide, and combinations thereof, and reacting the reactant stream in the presence of a catalyst at a temperature from about 200° C. to about 600° C. to produce a product stream comprising the trifluoroiodomethane.
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Paragraph 0053-0055
(2020/03/09)
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- ONE STEP PROCESS FOR MANUFACTURING TRIFLUOROIODOMETHANE FROM TRIFLUOROACETYL HALIDE, HYDROGEN, AND IODINE
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The present disclosure provides a process for producing trifluoroiodomethane (CF3I). The process includes providing vapor-phase reactants including trifluoroacetyl halide, hydrogen, and iodine, heating the vapor-phase reactants, and reacting the heated vapor-phase reactants in the presence of a catalyst to produce trifluoroiodomethane. The catalyst includes a transition metal.
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Paragraph 0048-0050
(2020/08/30)
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- PROCESSES FOR PRODUCING TRIFLUOROIODOMETHANE USING METAL TRIFLUOROACETATES
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The present disclosure provides a process for producing trifluoroiodomethane. The process includes providing a metal trifluoroacetate, iodine, a phase transfer catalyst, and an organic solvent, and reacting the metal trifluoroacetate and iodine in the presence of the phase transfer catalyst and the organic solvent to produce trifluoroiodomethane.
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Paragraph 0025-0030
(2020/09/19)
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- PROCESSES FOR PRODUCING TRIFLUOROIODOMETHANE USING METAL TRIFLUOROACETATES
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The present disclosure provides a process for producing trifluoroiodomethane. The process includes providing a metal trifluoroacetate, an iodine source, a metal catalyst, and a solvent, and reacting the metal trifluoroacetate and the iodine source in the presence of the metal catalyst and the solvent to produce trifluoroiodomethane. The metal catalyst includes at least one selected from the group of ferrous chloride and zinc (II) iodide.
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Page/Page column 0033-0036
(2020/09/19)
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- PROCESSES FOR PRODUCING TRIFLUOROIODOMETHANE AND TRIFLUOROACETYL IODIDE
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The present disclosure provides a process for producing trifluoroiodomethane, the process comprising providing a reactant stream comprising hydrogen iodide and at least one trifluoroacetyl halide selected from the group consisting of trifluoroacetyl chloride, trifluoroacetyl fluoride, trifluoroacetyl bromide, and combinations thereof, reacting the reactant stream in the presence of a first catalyst at a first reaction temperature from about 25° C. to about 400° C. to produce an intermediate product stream comprising trifluoroacetyl iodide, and reacting the intermediate product stream in the presence of a second catalyst at a second reaction temperature from about 200° C. to about 600° C. to produce a final product stream comprising the trifluoroiodomethane.
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Paragraph 0102-0118
(2020/03/09)
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- Production method of fluoroalkyl iodide
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The invention discloses a production method of a fluoroalkyl iodide, and particularly discloses a production method of a fluoroalkyl iodide as shown in a formula (I) as shown in the specification. Theproduction method of the fluoroalkyl iodide as shown in the formula (I) as shown in the specification comprises the following step: in a first solvent, subjecting a compound as shown in a formula (II) as shown in the specification and an iodide to an iodination reaction as shown in the specification. The raw materials used in the method are easy to obtain, and prices are low; and the method is high in conversion rate and yield, and the tolerability to functional groups is high.
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Paragraph 0112-0114
(2020/02/18)
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- Catalysts and integrated processes for producing trifluoroiodomethane
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The present disclosure provides a process for producing trifluoroiodomethane (CF3I). The process may include providing a vapor-phase reactant stream comprising trifluoroacetic acid and iodine and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising the trifluoroiodomethane. The catalyst includes silicon carbide.
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Page/Page column 10-12
(2020/07/07)
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- Method for industrially producing trifluoroiodomethane
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The invention discloses a method for industrially producing trifluoroiodomethane. According to the method, an aluminate ionic liquid is used as a solvent and a catalyst, so that the decarboxylation reaction and iodo reaction of trifluoroacetic acid are carried out under a same condition, and the selectivity of the trifluoroiodomethane is up to 95% or more; moreover, the step of alkalization of trifluoroacetic acid is omitted, so that the use of conventional liquid alkali is avoided, the discharge of wastewater and waste salt is reduced, the equipment cost is reduced, and benefit is brought tothe industrial production.
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Paragraph 0033; 0036-0037; 0038; 0041-0042; 0043-0057
(2019/04/04)
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- Metal-free and light-promoted radical iodotrifluoromethylation of alkenes with Togni reagent as the source of CF3 and iodine
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A light-promoted methodology for the iodotrifluoromethylation of alkenes was developed. For the first time a Togni reagent was exploited as the source of both the CF3 group and iodine atom. Preliminary mechanistic studies suggest that both CF3I and 2-iodobenzoic acid are direct sources of the iodine atom that is transferred to the products.
- Beniazza, Redouane,Douarre, Maxime,Lastécouères, Dominique,Vincent, Jean-Marc
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supporting information
p. 3547 - 3550
(2017/03/31)
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- Copper(I)-photocatalyzed trifluoromethylation of alkenes
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Using the photoreducible CuII precatalyst 2, trifluoromethylation reactions of alkenes are conducted effectively at low copper loading (0.1-0.5 mol%) on exposing the reaction mixture to sunlight/ambient light.
- Beniazza,Molton,Duboc,Tron,McClenaghan,Lastécouères,Vincent
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supporting information
p. 9571 - 9574
(2015/06/08)
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- Preparation of trifluoroiodomethane via vapor-phase catalytic reaction between hexafluoropropylene oxide and iodine
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Based on our previous investigation on the reaction mechanism to produce difluorocarbene and subsequent CF3I starting with CHF3 and I2, a new route for preparing CF3I at a relative low temperature, 200 °C, has b
- Yang, Guang-Cheng,Jia, Xiao-Qing,Pan, Ren-Ming,Quan, Heng-Dao
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experimental part
p. 985 - 988
(2010/02/28)
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- METHOD FOR PRETREATING AND REGENERATING CATALYSTS USED IN A PROCESS FOR MAKING FLUOROIODOALKANES
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A process for the preparation of a fluoroiodoalkane represented by the structural formula CF3(CF2)n—I, wherein n is 0 or 1. The process has the step of reacting a source of iodine with a compound represented by the structural formula CF3(CF2)n—Y, wherein Y is selected from H, Cl, Br and COOH and wherein n is 0 or 1. The reaction is carried out at a temperature from about 100° C. to about 750° C. and at a pressure from about 0.001 to about 100 atm for a contact time from about 0.001 second to about 300 hours in the presence a catalyst. The catalyst is subject to one or both of the following: (a) treating the catalyst prior to the reaction via contact with a gas selected from the group consisting of hydrogen fluoride, trifluoromethane, hydrogen, hydrogen iodide, iodine, fluorine, and oxygen, wherein the contact is carried out at a temperature and for a contact time sufficient to reduce the length of the induction period of the catalyst; and (b) treating the catalyst after the reaction via contact with a gas selected from the group consisting of hydrogen fluoride, hydrogen, fluorine, oxygen, or air at a temperature and for a contact time sufficient to regenerate the catalyst.
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Page/Page column 3-4
(2009/06/27)
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- Catalyst for the synthesis of CF3I and CF3CF2I
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A process for the preparation of a fluoroiodoalkane compound represented by the formula: CF3(CF2)n—Y, wherein n is 0 or 1. The process includes contacting A, B and C. A is represented by the formula: CF3(CF2)n—Y, wherein n is 0 or 1, and Y is selected from the group consisting of: H, Cl, Br, and COOH. B is a source of iodine, and C is a catalyst containing elements with d1s1 configuration and lanthanide elements. The process occurs at a temperature, and for a contact time, sufficient to produce the fluoroiodoalkane compound.
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Page/Page column 2
(2008/12/08)
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- A new method for the synthesis of trifluoromethylating agents-Diaryltrifluoromethylsulfonium salts
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A new synthetic method has been developed to prepare diaryltrifluoromethylsulfonium salts from diaryldifluorosulfuranes by the action of Me3SiCF3/F-. This reaction is the transformation of nucleophilic trifluoro-methylating reagent into electrophilic one.
- Yagupolskii, Lev M.,Matsnev, Andrej V.,Orlova, Raisa K.,Deryabkin, Boris G.,Yagupolskii, Yurii L.
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p. 131 - 136
(2008/09/21)
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- Catalyst promoters for producing trifluoroiodomethane and pentafluoroiodoethane
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The present invention provides a process for the preparation of a fluoroiodoalkane compound represented by the formula CF3(CF2)n—I, wherein n is 0 or 1. The process includes the step of contacting: (i) a compound represented by the formula CF3(CF2)n—Y, wherein Y is selected from H, Cl, Br, and COOH and n is 0 or 1; (ii) a source of iodine; (iii) an alkali or alkaline earth metal salt catalyst supported on a carrier; and (iv) a catalyst promoter for the alkali or alkaline earth metal salt catalyst. The catalyst promoter includes at least one element selected from a transition metal element, a rare earth metal element, a main group element other than the alkali or alkaline earth metal element, any salts thereof, and any combinations thereof. The contacting is carried out at a temperature and pressure and for a length of time sufficient to produce the fluoroiodoalkane compound. The contacting may be carried out in the presence or absence of a solvent and in the presence or absence of oxygen.
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Page/Page column 3-4
(2008/12/04)
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- Practical and efficient synthesis of perfluoroalkyl iodides from perfluoroalkyl chlorides via modified sulfinatodehalogenation
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A novel two-step one pot synthesis of perfluoroalkyl iodides (α,ω-diiodoperfluoroalkanes) from perfluoroalkyl chlorides (α-chloro-ω-iodoperfluoroalkanes) has been developed by initial conversion to the corresponding sodium perfluoroalkanesulfinates with sodium dithionite and then subsequent oxidation by iodine.
- Cao, Hai-Ping,Chen, Qing-Yun
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p. 1187 - 1190
(2008/02/10)
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- One-step synthesis of CF3-1
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A process for the preparation of trifluoromethyl iodide is provided. The process includes the step of contacting in a reactor a compound represented by the formula: [in-line-formulae]CF3—W[/in-line-formulae]and a compound represented by the formula: [in-line-formulae]IFn [/in-line-formulae]wherein W can be H, Br, Cl, COOH, COCl, COOCH3, COOC2H5, COCH3, COPh, CF3, Si(CH3)3, SPh, SCH3, SSCF3, SSPh, SSCH3, or SO2Cl, wherein n is 1, 3, 5, or 7, and wherein the step of contacting is carried out, at a temperature, pressure and for a length of time sufficient to produce trifluoromethyl iodide. The contacting step can be carried out in the presence or absence of a catalyst and the contacting step can be carried out in the presence or absence of air.
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Page/Page column 6
(2008/06/13)
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- DIRECT ONE-STEP SYNTHESIS OF CF3-I
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The present invention provides a process for the preparation of trifluoromethyl iodide. The process includes the step of: contacting in a reactor a compound represented by the formula: [in-line-formulae]CF3—W [/in-line-formulae] and a compound represented by the formula: [in-line-formulae]Z-I [/in-line-formulae] wherein W is selected from CF3, hydrogen and bromine; Z is selected from hydrogen, iodine and chlorine. The step of contacting is carried out, optionally in the presence of a catalyst and further optionally in the presence of air, at a temperature, pressure and for a length of time sufficient to produce the trifluoromethyl iodide.
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Page/Page column 3
(2008/06/13)
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- Direct one-step synthesis of trifluoromethyl iodide
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A catalytic one-step process for the production of CF3I by reacting, preferably in the presence of a source of oxygen, a source of iodine with a reactant of the formula: [in-line-formulae]CF3R[/in-line-formulae] where R is —SH, —S—S—CF3, —S-phenyl, or —S—Si—(CH3)3. The catalyst may be a metal salt such as salts of Cu, Hg, Pt, Pd, Co, Mn, Rh, Ni, V, TI, Ba, Cs, Ca, K and Ge and mixtures thereof, preferably on a support such as MgO, BaO and CaO, BaCO3, CsNO3, Ba (NO3)2, activated carbon, basic alumina, and ZrO2.
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(2008/06/13)
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- Fluoroform: An efficient precursor for the trifluoromethylation of aldehydes
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Fluoroform is shown to be an efficient trifluoromethylating agent when deprotonated using standard reagents in DMF. The important role of DMF as a solvent but also as a reactant was demonstrated.
- Folléas, Beno?t,Marek, Ilan,Normant, Jean-F.,Saint-Jalmes, Laurent
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p. 275 - 283
(2007/10/03)
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- Reactivity of Negative Ions with Trifluoromethyl Halides
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The kinetics of the reactions of selected anions (A(-)) with the trifluoromethyl halides CF3X (X = F, Cl, Br, I) in the gas phase were measured at 300 K.Reaction rate constants and product branching fractions were determined using a selected ion flow tube (SIFT) instrument.The chosen anions were C5F5N(-), o-, m-, and p-CF3C6H4CN(-), C6F5Br(-), C6F5Cl(-), C6F5CF3(-), C6F5COCH3(-), Fe(-), FeCO(-), SF6(-), SO(-), SO2(-), NO(-), NO2(-), and NO3(-).The reactivity of these systems varies from unreactive to collisional, and a variety of reaction types was found.The results of our present and previous measurements on A(-) + CF3X reactions show that, in cases where nondissociative electron transfer (NDET) is energetically allowed, the total reactivity tends to be high, approaching collisional.This suggests that reactivity in these cases is initiated and controlled by electron transfer from the anion.In addition, association reactions tend to be preempted when NDET is energetically allowed.A few exceptions to these tendencies were found and are discussed.
- Morris, Robert A.,Viggiano, A. A.,Miller, Thomas M.,Seeley, John V.,Arnold, Susan T.,et al.
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p. 10641 - 10645
(2007/10/03)
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- Facile conversion of perfluoroacyl fluorides into other acyl halides
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Nine perfluoroacyl fluorides underwent halogen exchange when treated with anhydrous lithium halides to give acyl chlorides, bromides and iodides in high yields. The temperature dependence of this reaction is described. In the reaction with perfluorodiacyl fluoride, the diacyl halides possessing different acyl halide-groups were also produced. Of the alkaline metal salts used halogen exchange was successful only with lithium salts because of the interaction between lithium and fluorine.
- Fukaya, Haruhiko,Matsumoto, Tomonori,Hayashi, Eiji,Hayakawa, Yoshio,Abe, Takashi
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p. 915 - 920
(2007/10/03)
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- LASER-INDUCED DECOMPOSITION OF HEPTAFLUORO-2-IODOPROPANE
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CO2 laser-induced homogeneous decomposition of i-C3F7I yields a variety of perfluorinated compounds, which are suggested to be formed by recombinations of carbenes and radicals generated upon the cleavage of the C-1 bond and the fragmentation of the i-C3F7 radical.The decomposition of i-C3F7I in the presence of ethene leads mainly to the formation of (i-C3F7CH2)2 and i-C3F7(CH2)2I.
- Pola, Josef,Horak, Milan
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p. 121 - 124
(2007/10/02)
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- Gas-phase reactions of oxide and superoxide anions with CF4, CF3Cl, CF3Br, CF3I, and C2F4 at 298 and 500 K
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Rate constants and product branching fractions have been measured for the gas-phase reactions of oxide (O-) and superoxide (O2-) anions with the halocarbons CF4, CF3Cl, CF3Br, CF3I, and C2F4 using a variable temperature-selected ion flow tube (VT-SIFT) instrument operated at 298 and 500 K.The reactions of O- with CF3X (X = Cl, Br, I) are fast and produce F-, XF-, and XO- for all X.For CF3Cl and CF3Br, X- is also formed.For CF3I, CF3- and IOF- are minor products.O- reacts rapidly with C2F4 producing F- as the major ionic product, along with contributions from reactive detachment and minor formation of FCO-, CF3-, and C2F3O-.The reaction of O2- with CF3Cl is slow, and both clustering and X- formation were observed.For CF3Br and CF3I, the reactions with O2- are fast, and nondissociative charge transfer was observed in addition to X- formation.O2- reacts rapidly with C2F4 by reactive detachment, in addition to producing F- as the major ionic product with smaller amounts of F2-, FCO-, FCO2-, CF3O-, and C2F4O-.O- and O2- were both found to be unreactive with CF4 at 298 and 500 K.The efficiencies of the reactions of both O- and O2- with CF3X are greater for the heavier halides at both 298 and 500 K.The rate constants for the reactions of O2- with CF3X appear to correlate both with the rates of thermal electron attachment to CF3X and with the electron affinities of CF3X, indicating that the O2- + CF3X reaction mechanism may involve initial electron transfer followed by dissociation.Thus the negative electron affinity of CF3Cl may explain the very slow rate for reaction with O2- despite the available exothermic pathways.
- Morris, Robert A.
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p. 2372 - 2381
(2007/10/02)
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- Reactions of Ar+ with halocarbons and of I+ with CF3I
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The gas phase reactions of Ar+ with the halocarbons CF3Cl, CF3Br, CF3I, CF4, C2F6, and C2F4 have been studied using a variable temperature-selected ion flow tube (VT-SIFT) instrument operated at 298 and 500 K.Rate constants and product branching percentages were measured at both temperatures.Ar+ reacts at the collisional rate with all of the above neutrals at both 298 and 500 K.The reactions with CF3X yield CF3+ and CF2X+ for all X (the reaction with CF4 produces only CF3+).For X = I, there is an additional channel leading to the ionic product I+.The reaction of Ar+ with C2F6 produces both CF3+ and C2F5+.The reaction of Ar+ with C2F4 forms a rich product spectrum consisting of the ions CF+, CF2+, CF3+, C2F3+, and C2F4+.The reaction product distributions are compared with results from ionization experiments such as photoion-photoelectron coincidence (PIPECO) and electron impact mass spectrometry, and in some cases excellent agreement is found.The reaction of I+ with CF3I, which is a secondary reaction in the Ar+/CF3I system, was investigated at 298 K in separate experiments.This reaction is rapid and forms four product ions: CF3+, CF2I+, CF3I+, and I2+.The results are compared with previously published information.
- Morris, Robert A.,Doren, Jane M. Van,Viggiano, A. A.,Paulson, John F.
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p. 173 - 179
(2007/10/02)
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- Chemistry of H2O+ with C2F4, C2F6, and CF3X (X = F, Cl, Br, I)
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The reactions of H2O+ with CF4, C2F6, C2F4, CF3Cl, CF3Br, and CF3I have been studied at 300 and 499 K.The measurements were conducted using a variable-temperature-selected ion flow tube apparatus.H2O+ reacts via charge transfer with C2F4 with rate constants equal to 1.4 x 10-9 and 1.5 x 10-9 cm3 s-1 at 300 and 499 K, respectively.The reactions with CF3X (X = Cl, Br, I) all proceed at the collision rate at 300 and 499 K within experimental uncertainty.The rate constants are in the range 1.6 x 10-9 - 2.1 x 10-9 cm3 s-1.The reactions of H2O+ with CF3X produce CF3+ and CF2X+ for X = Cl, Br, I, CF2OH+ for X = Cl, Br, and CF3X+ for X = Br, I.The reaction with CF3Cl also forms the ionic product CF3OH2+.No reaction was observed between H2O+ and the reactant neutrals CF4 and C2F6; the rate constants are less than 5 x 10-12 cm3 s-1 at 300 and 499 K.Upper limits to the heats of formation of CF2Cl+, CF2Br+, and CF2I+ have been derived from the data and are -1, respectively.
- Morris, Robert A.,Viggiano, A. A.,Doren, Jane M. Van,Paulson, John F.
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p. 3051 - 3054
(2007/10/02)
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- Chemistry of CFn(1+) (n = 1-3) Ions with Halocarbons
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The gas-phase reactions of CF(1+), CF2(1+), and CF3(1+) with the halocarbons CF3Cl, CF3Br, CF3I, CF4, and C2F6 have been studied using a variable-temperature-selected ion flow tube (VT-SIFT) instrument at 300 and 496 K.The ion CF(1+) reacts rapidly with CF3X (X = Cl, Br, I) producing the ions CF2X(1+).In the reaction of CF(1+) with CF3Cl, CF3(1+) is also produced as a minor product.Curvature was observed in the pseudo-first-order kinetics plots for the reactions of CF(1+) with CF4 and C2F6.In both cases the curvature is attributed to the presence of two or more CF(1+) states (probably vibrational) of differing reactivities toward the perfluorocarbon of interest.This conclusion is supported by our observation of charge transfer from CF(1+) to NO, a reaction which is endothermic by 15 kJ/mol for the ground state of CF(1+).CF(1+) is unreactive with O2, N2, and Xe.The reactions of CF2(1+) with CF3X yield CF3(1+) and CF2X(1+) for X = Cl and Br; for X = I, CF2I(1+) and CF3I(1+) are produced.The overall reactions proceed at approximately the collision rate at 300 and 496 K, and the branching ratios are not strongly dependent on temperature.The reactions of CF2(1+) with CF4 and C2F6 produce CF3(1+) and C2F5(1+), respectively.The rate constants decrease significantly with increasing temperature.CF2(1+) reacts rapidly by charge transfer with NO.The reaction of CF2(1+) with O2, producing CF2O(1+), is inefficient.CF2(1+) is unreactive with N2.CF3(1+) reacts with CF3X (X = Cl, Br, I) at rates below the collision values, producing a single ionic product, CF2X(1+).While the rate constants for the reactions of CF3(1+) with CF3X increase in the series with increasing CF3X mass, the rate constants for reaction with each CF3X decrease sharply with increasing temperature.A mechanism is proposed in which the reaction proceeds on a double-well potential energy surface.No reaction was observed for the CF3(1+)/CF4 system.CF3(1+) appeared to react very slowly with C2F6 and NO, producing C2F5(1+) and NO(1+), respectively, but reactions with impurities in the neutral reagents cannot be ruled out as the source of these ions.CF3(1+) is unreactive with O2 and N2.
- Morris, Robert A.,Viggiano, A. A.,Doren, Jane M. Van,Paulson, John F.
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p. 2597 - 2603
(2007/10/02)
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- Iodine Atoms and Iodomethane Radical Cations: Their Formation in the Pulse Radiolysis of Iodomethane in Organic Solvents, Their Complexes, and Their Reactivity with Organic Reductants
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Pulse radiolysis of iodomethane in various organic solvents leads to formation of iodine atoms or iodomethane radical cations, which in turn form complexes with iodomethane or with the solvent.Radiolysis in cyclohexane gives CH3I*I, which exhibits an absorption peak at 390 nm, whereas radiolysis in benzene forms the solvent complex, C6H6*I, which exhibits an intense broad absorption centered at 490 nm.Radiolysis of iodomethane in acetone, benzonitrile, and halogenated hydrocarbons results in formation of the radical cation CH3I.+.In the former two solvents, this species forms a complex with another molecule of iodomethane to give (CH3))2+, which absorbs at 420 nm, in agreement with previous results in aqueous solutions, but in halogenated hydrocarbons it forms complexes with the solvents, absorbing at 320-360 nm, i.e. near the absorption of monomeric CH3I.+ in water.Complexes of I atoms oxidize phenol and triphenylamine relatively slowly whereas complexes of CH3I.+ react more rapidly.The reactivity of the CH3I.+*RX complexes increases in the order of RX = CH2Cl2, CHCl3, CH2Br2, CCl4, CH3I, and for each complex the reactivity with phenol increases with increase in electron donating power of substituents.Replacing the methyl group of iodomethane radical cation with ethyl or isopropyl decreases the reactivity, whereas trifluoromethyl increases the reactivity.These oxidation reactions proceed via an intermediate complex between the iodine species and the organic reductant.
- Shoute, Lian C. T.,Neta, P.
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p. 4411 - 4414
(2007/10/02)
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- Polar trifluoromethylation reactions: the formation of bis(trifluoromethyl)iodine(III) compounds and trifluoromethyl iodine(III) cations and anions
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IX3 (X = Cl, OCOCF3, ONO2) reacts with Cd(CF3)2 complexes or Bi(CF3)3 to yield the corresponding CF3IX2 derivatives. 19F nuclear magnetic resonance spectroscopic evidence is found for + and I(CF3)2X (X = Cl, OCOCF3) in the reactions of CF3IX2 with Cd(CF3)2 complexes.During the reaction of CF3IF2 and Hg(CF3)2 the new species I(CF3)2F and cis-- are identified by nuclear magnetic resonance spectroscopy.The reactions proceed under polar conditions and can be accelerated by the addition of a Lewis acid such as BF3, B(OCOCF3)3, or Sb(V) compounds.Difluoromethyl compounds are formed as by-products.Key words: polar trifluoromethylations, trifluoromethyl iodine(III) compounds, difluoromethyl group formation.
- Tyrra, Wieland,Naumann, Dieter
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p. 327 - 333
(2007/10/02)
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- Power-variable trifluoromethylating agents, (trifluoromethyl)dibenzothio- and -selenophenium salt system
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(Trifluoromethyl)dibenzothio- and -selenophenium triflates and their nitro derivatives differing in trifluoromethylating power were developed as a new system of electrophilic trifluoromethylating agents.
- Umemoto,Ishihara
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p. 3579 - 3582
(2007/10/02)
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- Convenient Synthesis of N-Containing Perfluoroalkyl Iodides
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Some new nitrogen-containing perfluoroalkyl iodides were synthesized directly by the reaction of corresponding perfluoroacid fluorides with lithium iodide in high yield.
- Fukaya, Haruhiko,Abe, Takashi,Hayashi, Eiji
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p. 813 - 814
(2007/10/02)
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- REACTIONS OF TeF5OCl WITH FLUOROCARBON IODIDES AND SYNTHESIS OF CF3OTeF5
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The low temperature reaction of TeF5OCl with the fluorocarbon iodides, CF3I, C2F5I, n-C3F7I, and i-C3F7I results in the formation of RfI(OTeF5)2 adducts.Except for the trifluoromethyl derivative these are stable, colorless compounds.The trifluoromethyl adduct decomposes above -78 deg C to give the previously unknown CF3OTeF5.The perfluoroethyl and n-propyl adducts decompose at 120 deg C or under UV radiation giving C2F5OTeF5 and n-C3F7OTeF5, respectively.These reactions constitute a new synthesis of primary RfOTeF5 compounds.Attempts to extend this synthesis to secondary fluorocarbon iodides were unsuccessful.
- Schack, Carl J.,Christe, Karl O.
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- TRIFLUORMETHYLIERUNGSREAKTIONEN VON Te(CF3)2 MIT HALOGENBENZOLEN UND METHYLBENZOLEN
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Substituent effects on yields and regioselectivity of photochemical and thermal trifluoromethylation reactions of Te(CF3)2 with halogen benzenes and methyl benzenes are investigated under comparable conditions.All reactions lead to trifluoromethylated products.The yields of the thermal are always higher than those of the corresponding photochemical reactions.The reactivity of the halobenzenes increases in the series C6H5-F a sidereaction, but H-substitution is the primary reaction pathway.During the reactions with iodobenzene tellurium containing compounds are also formed.The reactions with methyl benzenes show an increase in reactivity in the series hexamethylbenzene mesitylene toluene p-xylene.In all cases only ring substituted products are detected.Reactions with toluene and p-xylene yield tellurium containing compounds as well as addition products.The 19F-n.m.r spectra of the products are given.
- Naumann, Dieter,Kischkewitz, Jurgen
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p. 283 - 299
(2007/10/02)
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- THERMOLYSIS AND UV-PHOTOLYSIS OF PERFLUORINATED IODO-ALKANES AND IODO-OXAALKANES: THERE IS A PREFERRED REACTION CHANNEL
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The thermal stability of perfluorinated iodides depends on their structure and decreases in the order of RFCF2CF2I>RFCF2CF(CF3)I>RFOCF(CF3)I=RFCF2C(CF3)2I.The major decomposition path consists of the elimination of an unsaturated compound (CF2=CF2, CF2=CF-CF3, O=CF-CF3, CF2=C(CF3)2, respectively) with concomitant formation of RFI.The highest selectivities were found for tertiary iodides and 2-iodo-3-oxaalkanes, whose decomposition is virtually irreversible.UV-photolysis of the iodo-compounds gave the same products as the thermolysis reactions.
- Probst, Anton,Werner, Konrad von
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p. 163 - 173
(2007/10/02)
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- ON SOME NEW TRIFLUOROMETHYL IODINE(III) COMPOUNDS: REACTIONS OF CF3IF2 WITH BORON AND SILICON COMPOUNDS AND CF3ICl2 WITH SILVER SALTS
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CF3IF2 undergoes fluorine exchange reactions with BX3 (X = Cl, Br, I, OCOCF3) to form the compounds CF3IX2.The reactions of CF3IF2 with (CF3)2BN(CH3)2, (CH3)3SiNCO and (CH3)3SiN(CH3)COCF3 yield the corresponding new trifluoromethyl iodine (III) nitrogen compounds.A preparative method for the synthesis of CF3ICl2 is found by reacting CF3IF2 with (CH3)3SiCl.CF3ICl2 reacts with AgX (X = OCOCF3, SCF3) to yield the corresponding CF3IX2 compounds and with (C6H5)4AsCl the novel ion (-) is detected.Products were identified by n.m.r. spectroscopy.
- Tyrra, Wieland,Naumann, Dieter
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p. 401 - 416
(2007/10/02)
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- Synthesis and characterization of (trifluoromethyl)gold complexes
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The synthesis of (CF3)AuL (L = PMe3, PEt3, PPh3) from LAuCl and Cd(CF3)2·DME is described. These linear gold(I) compounds readily add excess halogen to form the predominantly trans square-planar gold(III) dihalides (CF3)AuX2(L) (X = Br, I). The use of stoichiometric (or less) halogen leads to a significant quantity of (CF3)2AuX(L) (L = PMe3, PEt3) which is shown to arise from trifluoromethyl/halogen ligand exchange between (CF3)AuL and (CF3)AuX2(L). No evidence for ligand exchange is found when L = PPh3. (CF3)2AuI(L) (L = PMe3, PEt3) may also be prepared in 80% yield from the oxidative addition of trifluoromethyl iodide to (CF3)AuL; experiments with the radical scavenger galvinoxyl suggest a radical chain mechanism for this CF3I addition. Close examination of the 1H and 19F NMR spectra for the new square-planar complexes reveals that downfield shifts occur for both nuclei when a cis halide is changed from Br to I; a trans halide causes an upfield shift upon this substitution. The cadmium reagent is, in general, ineffective for the preparation of Au(III) complexes since reduction to (CF3)AuL usually occurs. However, treatment of (CF3)2AuI(PMe3) with Cd(CF3)2·DME in the presence of excess CF3I leads to the high-yield synthesis of the tris(trifluoromethyl) species (CF3)3AuPMe3.
- Sanner, Robert D.,Satcher Jr., Joe H.,Droege, Michael W.
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p. 1498 - 1506
(2008/10/08)
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- Preparation of bis(trifluoromethyl)tellurium, bis(trifluoromethyl)selenium, bis(trifluoromethyl)diselenium, tris(trifluoromethyl)antimony, tris(trifluoromethyl)arsine, bis(trifluoromethyl)arsenic iodide, tris(trifluoromethyl)phosphine, and (trifluoromethyl)phosphorus diiodide by reaction of bis(trifluoromethyl)mercury with the group 5 and 6A (15 and 16) halides
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The reactions between Hg(CF3)2 and representative halides of the lower elements of main groups 5 (15) and 6A (16) have been investigated. At 155°C the reaction between TeBr4 and Hg(CF3)2 affords Te(CF3)2 in 92% yield. In 4.5 h at 210°C SeBr4 and Hg(CF3)2 form Se(CF3)2 and Se2(CF3)2 in 67% and 3% yields, respectively; in 2.5 h at 170°C they generate Se(CF3)2 and Se2(CF3)2 in 26% and 57% yields, respectively. At 165°C SbI3 and Hg(CF3)2 produce Sb(CF3)3, 63%. The interaction of AsI3 and Hg(CF3)2 can result in either As(CF3)3, 75%, or As(CF3)2I, 54%. Similarly, exposure of PI3 to Hg(CF3)2 can synthesize either P(CF3)3, 55%, or P(CF3)I2, 37%. In general, these reactions are more convenient than the classic route pioneered by Emeleus and his students, the interactions of trifluoromethyl iodide with the elements.
- Ganja, Edward A.,Ontiveros, Cynthia D.,Morrison, John A.
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p. 4535 - 4538
(2008/10/08)
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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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- Halogen nitrates
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The low-temperature infrared and Raman spectra of I(NO3)3 and the Raman spectra of liquid ClONO2, FONO2, FNO2, and ClNO2 have been recorded. Comparison of the vibrational spectra within the series NO2, FNO2, ClNO2, FONO2, and ClONO2 allows unambiguous assignments for the halogen nitrate molecules. Raman polarization measurements show that in halogen nitrates the halogen atom is perpendicular to the ONO2 plane contrary to previous assumptions and to the known planar structure of HONO2 and CH3ONO2. The vibrational spectrum of I(NO3)3 is consistent with predominantly covalent nitrato ligands. However, the complexity of the spectrum suggests a polymeric structure with bridging nitrato groups. Experimental evidence was obtained for the formation of the new and thermally unstable compound CF3I(NO3)2 in the CF3I-CIONO2 system. Attempts to convert this compound into CF3ONO2 were unsuccessful.
- Christe, Karl O.,Schack, Carl J.,Wilson
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p. 2811 - 2815
(2008/10/08)
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