Trichlorofluoromethane, reaction

Under anaerobic conditions, various reactions can occur, and the following are illustrative (a) trichlorofluoromethane -> carbon monoxide (b) hexachloroethane tetrachlo-roethene (c) l,l,l-trichloro-2,2,2-trifluoroethane l,l-dichloro-2,2-difluoroethene (Hur et al. 1994). 

Irradiation at 77 K in trichlorofluoromethane of cyclic tertiary amines also affords radical cations that can be trapped indefinitely. In these systems there apparently is no reaction between the radical cations and free amine. The EPR spectra of the radical cations were recorded. The cations produced under these conditions can be trapped indefinitely and do not undergo proton loss to give the corresponding carbon-centred radical. Several systems (20-24) were examined in this way and all were found to be stable. In the bis amine (22, n = 1) evidence was obtained from the EPR study that there was weak N-N interaction4. The influence of silicon in 25 was also examined16. 

Bromine monofluoride or iodine monofluoride can be prepared from the corresponding elements in trichlorofluoromethane at — 781 and — 45 C,2,3 respectively. The compounds are unstable and decompose at low temperatures, iodine monofluoridc at — 14 C2,3 and bromine monofluoride, in part, even at — 78 C.1 Therefore, they are used, without separation and purification, in Freon solutions at low temperatures or, most frequently, as stoichiometric mixtures bromine trifluoride/bromine and iodine pentafluoride/iodine. A solution of iodine monofluoride, obtained by bubbling nitrogen-diluted fluorine gas into a suspension of iodine in trichlorofluoromethane at — 75 C, was used for addition to alkene C = C bonds. The reaction is regioselective and in most cases obeys the Markovnikov rule.4 Iodine monofiuoride prepared in situ reacts quite efficiently with steroidal alkenes.4... 

When diphenylacetylene dissolved in cold chloroform reacts with iodine monofluoride suspended in trichlorofluoromethane, the iodine atoms in the primary addition product are easily replaced by fluorine to give l,1,2,2-tetrafluoro-1,2-diphenylethane (60%) along with benzil (10%). Since the C —Br bond is stronger than the C —I bond, the reaction of bromine monofluoride with diphenylacetylene gives 1,1-dibromo-2,2-difluoro-1,2-diphenylethane (65%) and benzil (15%). 

Trifluoromethyl hypofluorite reacts with various sulfides in trichlorofluoromethane at — 78 C forming difluoro- 624 and tctrafluorosulfancs 7,25 while fluorodesulfuration is observed in the reaction of amino acids, e.g. formation of 8.26 In a similar manner, trivalent phosphorus compounds react with trifluoromethyl hypofluorite to give difluoro-substituted derivatives 9.27... 

V-Fluorobis(phenylsulfonyl)amine (1 a) can be synthesized in a one-step reaction using commercially available bis(phenylsulfonyl)amine (up to 0.2 mol) and fluorine (10% F2/N2,1 equiv) in the presence of powdered sodium fluoride, either in acetonitrile at — 40 °C in an ambient pressure reactor131 or in trichlorofluoromethane/chloroform, water or a water-miscible organic solvent.133 iV-Fluorobis(phenylsulfonyl)amine (la) is soluble in most organic solvents, e.g. diethyl ether, tetrahydrofuran, dichloromethane. acetonitrile and toluene.131 133... 

The reaction of compounds C6F5R with vanadium(V) fluoride at — 25 to — 30 C in sulfuryl chloride fluoride or trichlorofluoromethane solution yields 1-substituted heptafluorocyclo-hexadienes and nonafluorocyclohexenes with the former predominating (see Table 5).113-115... 

Hexachloroacetone is fluorinated87 over potassium tetrafluorocobaltate(III) at 230°C. As with nonchlorinated ketones (Section 25.1.1.3.), no ketonic products are detected, and low yields of trichlorofluoromethane, methyl dichlorofluoroacetate (the reaction mixture is worked up by methanol treatment) and methyl trichloroacetate are isolated. 

Most of the investigations into disproportionation reactions have mainly concentrated on chlorofiuoro derivatives of methane and ethane. When trichlorofluoromethane is refluxed with aluminum trichloride or aluminum tribromide, dichlorodifluoromethane and carbon tetrachloride are obtained. Dichlorofluoromethane yields chlorodifiuoromethane and chloroform chlorofiuoro derivatives of ethane and longer chain homologs exhibit a tendency towards isomerization as well as disproportionation, i.e. intramolecular halogen atom exchange. In this case, both types of reaction take place simultaneously. In other words, disproportionation of l,l,2-triehloro-1.2,2-trifiuoroethane (1) forms l,l,1.2-tetrachloro-2,2-difluoroethane (2) and... 

Atkinson, R., Hansen, D.A., Pitts Jr., J.N. (1975) Rate constants for the reaction of hydroxyl radicals with chlorodifluoromethane, dichlorodifluoromethane, trichlorofluoromethane and molecular hydrogen over temperature range 297 134 K. J. Chem. Phys. 63, 1703-1706. 

Dichlorodifluoromethane and Trichlorofluoromethane.60 In a flask connected to an ice-cooled reflux condenser, a mixture of 2 moles of carbon tetrachloride and 1 mole of antimony trifluoride is cooled to 0°. After addition of 0.1 mole of antimony pentachloride, the mixture is allowed to warm until the reaction starts. The reaction is regulated by intermittent cooling and heating in order not to overtax the reflux condenser. The uncondensed vapors are led to a receiver cooled with solid carbon dioxide. The distillate is a mixture of CCl3F(b.p. 25°) and CCl2F2(b.p. —30°) whose composition depends on the efficiency of the dephlegmation but is usually 50-50 in a laboratory operation. At the... 

Rozen and coworkers30 have also reported that acetonitrile can replace trichlorofluoromethane in the preparation and in situ reactions of acetyl hypofluorite without sacrificing the efficiency and the regio- and stereoselectivity of the addition of AcOF to olefins. Most other solvents investigated proved to be unsatisfactory for the synthesis of AcOF, despite the fact that fluorine does react with the dispersed sodium acetate present in the solvent. 

Bis[trifluoromethyl] tellurium and bis[pentafluorophenyl] tellurium react with dimethyl zinc or dimethyl cadmium with stepwise replacement of the perfluoroorganyl groups by methyl groups2,3. These reactions were carried out in trichlorofluoromethane in the presence of bis[2-ethoxyethyl] ether as the complexing agent for the perfluoroorgano element compounds2. 

In a jacketed tube reactor, 2.0 ml 30% fuming H2SO4 and 10 ml trichlorofluoromethane were cooled —25°C, 2.0 g difluoroamine condensed into the mixture, warmed to 10 °C to melt the acid layer, and the mixture re-cooled to — 15°C. The product from Step 8 (0.36 mmol) was added, the reaction tube sealed at — 15°C for 3 hours, then quenched in water. The solution was basified with NaHC03 to pH 12 and extracted 4 times with 100 ml CH2CI2. The solute was re-dissolved in CH2CI2, chloroform added, and the mixture concentrated. A precipitate formed and was re-dissolved in acetone, filtered through a medium porosity fritted filter, and the product isolated, mp = 208 °C (explodes). H-and C-NMR data supplied. 

The reaction of diazo compounds with an electrophilic fluorinating reagent, tri-fluoromethyl hypofluorite. has also been studied (Tabic 8, entries 9 13). ° The reactions are carried out at — 70 C using trichlorofluoromethane as solvent and mixtures of g /n-difluoro compounds and fluoro(trifluoromethoxy) derivatives are obtained. Although conversion is generally complete, the yields of isolated products are low, due to their difficult separation. In some cases (entries 9, 11, and 12), ketones and epoxides arc formed as byproducts. Consequently, this method is not a useful alternative for the preparation ofgcw-difluoro compounds. 

OcUfluorona rfithaleiie Hexafluororbeiuite(V). O tafluoronaphthalene (0.42 mmol) was dissolved in dry trichlorofluoromethane (0.5 mL) at 273 K in a fused silica vessel. A slight excess of rhenium hexafluoride was admitted to the reaction vessel, causing the deep green octafluoro-naphthalene hexafluororhenate(V) to precipitate at the vapor-liquid in-... 

Because the single covalent bonds are hard to break, catalysts are often added to the reaction mixture. For example, trichlorofluoromethane, CCI3F, commonly known as Freon-11, was used as a refrigerant. It was made by a substitution reaction catalyzed by SbF3. 

Foams may be prepared by either one of two fundamental methods. In one method, a gas such as air or nitrogen is dispersed in a continuous liquid phase (e.g. an aqueous latex) to yield a colloidal system with the gas as the dispersed phase. In the second method, the gas is generated within the liquid phase and appears as separate bubbles dispersed in the liquid phase. The gas can be the result of a specific gasgenerating reaction such as the formation of carbon dioxide when isocyanate reacts with water in the formation of water-blown flexible or rigid urethane foams. Gas can also be generated by volatilization of a low-boiling solvent (e.g. trichlorofluoromethane, F-11, or methylene chloride) in the dispersed phase when an exothermic reaction takes places, (e.g. the formation of F-11 or methylene chloride-blown foams). 

Carbonyl chloride fluoride is conveniently prepared from the reaction of the trichlorofluoromethane, CCI3F, with sulfur(IV) oxide ... 

A fairly efficient synthesis of 1-chloro-l-fluorocyclopropanes under mild conditions is based on the reduction of trichlorofluoromethane by a zerovalent titanium species in the presence of an alkene (Table 6). The metal is formed in the reaction system from titaniura(IV) chloride and lithium aluminum hydride. ... 

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