Fluorination with

For many years it was thought that fluorine did not form any 0x0-acids or oxo-acid anions. Recent work, however, indicates the existence of fluoric(I) acid (hypofluorous acid), HFO, formed by the reaction of fluorine with water at 273 K. The acid forms colourless crystals, m.p. 156 K, is very unstable and has, as expected, very strong oxidising properties. 

As already noted, the simple salts in this oxidation state are powerful oxidising agents and oxidise water. Since, also, Co(III) would oxidise any halide except fluoride to halogen, the only simple halide salt is C0F3. Cobalt(lll) Jluoride, obtained by reaction of fluorine with cobalt(II) fluoride it is a useful fluorinating agent. 

Fluorine is the most electronegative and reactive of all elements. It is a pale yellow, corrosive gas, which reacts with most organic and inorganic substances. Finely divided metals, glass, ceramics, carbon, and even water burn in fluorine with a bright flame. 

One hypothesis says that fluorine can be substituted for hydrogen wherever it occurs in organic compounds, which could lead to an astronomical number of new fluorine compounds. Compounds of fluorine with rare gases have now been confirmed in fluorides of xenon, radon, and krypton. 

The halogen fluorides are best prepared by the reaction of fluorine with the corresponding halogen. These compounds are powerful oxidising agents chlorine trifluoride approaches the reactivity of fluorine. In descending order of reactivity the halogen fluorides are chlorine pentafluoride [13637-63-3] 1 5 chlorine trifluoride [7790-91-2] 3 bromine pentafluoride [7789-30-2], BrF iodine heptafluoride [16921 -96-3], chlorine... 

Bromine Trifluoride. Bromine trifluoride is produced commercially by the reaction of fluorine with bromine ia a continuous gas-phase process where the ratio of fluorine to bromine is maintained close to 3 1. It is also produced ia a Hquid-phase batch reaction where fluorine is added to Hquid bromine at a temperature below the boiling poiat of bromine trifluoride. 

Rhenium heptafluoride [17029-21 -9], ReF, is obtained by the direct interaction of elemental fluorine with hydrogen-reduced rhenium powder at 400°C and slightly over atmospheric pressure of fluorine. It is a pale yeUow soHd, mol wt 319.19 mp, 48.3°C and bp, 73.7°C. 

Organic fluorine compounds were first prepared in the latter part of the nineteenth century. Pioneer work by the Belgian chemist, F. Swarts, led to observations that antimony(Ill) fluoride reacts with organic compounds having activated carbon—chlorine bonds to form the corresponding carbon—fluorine bonds. Preparation of fluorinated compounds was faciUtated by fluorinations with antimony(Ill) fluoride containing antimony(V) haUdes as a reaction catalyst. 

This reaction has often reached explosive proportions in the laboratory. Several methods were devised for controlling it between 1940 and 1965. For fluorination of hydrocarbons of low (1—6 carbon atoms) molecular weight at room temperature or below by these methods, yields as high as 80% of perfluorinated products were reported together with partially fluorinated species (9—11). However, fluorination reactions in that eta involving elemental fluorine with complex hydrocarbons at elevated temperatures led to appreciable cleavage of the carbon—carbon bonds and the yields invariably were only a few percent. 

Materials similar ia high temperature properties to the Du Pont material with better low temperature properties have been synthesized usiag direct fluofination. The first was produced by reaction of fluorine with iaexpensive hydrocarbon polyethers such as poly(ethylene oxide). In the simplest case, poly(ethylene oxide) is converted to the perfluoroethylene oxide polymer ... 

Fluorination with XeF2 or C H IF2 gives both the 1,2- and 1,4-difluoro products. This reaction proceeds via the initial electrophilic addition of F to the diene (53). 

At 225—275°C, bromination of the vapor yields bromochloromethanes CCl Br, CCl2Br2, and CClBr. Chloroform reacts with aluminum bromide to form bromoform, CHBr. Chloroform cannot be direcdy fluorinated with elementary flourine fluoroform, CHF, is produced from chloroform by reaction with hydrogen fluoride in the presence of a metallic fluoride catalyst (8). It is also a coproduct of monochlorodifluoromethane from the HF—CHCl reaction over antimony chlorofluoride. Iodine gives a characteristic purple solution in chloroform but does not react even at the boiling point. Iodoform, CHI, may be produced from chloroform by reaction with ethyl iodide in the presence of aluminum chloride however, this is not the route normally used for its preparation. 

In the presence of catalysts, trichloroethylene is readily chlorinated to pentachloro- and hexachloroethane. Bromination yields l,2-dibromo-l,l,2-trichloroethane [13749-38-7]. The analogous iodine derivative has not been reported. Fluorination with hydrogen fluoride in the presence of antimony trifluoride produces 2-chloro-l,l,l-trifluoroethane [75-88-7] (8). Elemental fluorine gives a mixture of chlorofluoro derivatives of ethane, ethylene, and butane. 

The enamines, enol ethers and enol acetates of A -3-keto steroids provide important substrates for fluorination with FCIO3. Reaction of such A -enol ethers and acetates (6) with perchloryl fluoride results in 6a- and 6jff-fluoro-A -3-ketones (7) and (8), the latter representing the more abundant isomer. Tetrahydrofuran or dioxane-water mixtures appear to be particu-... 

Trimethylarsine gives a 98% yield of trimethylarsine difluoride when treated with xenon difluoride [102] in fluorotrichloromelhane. and tnsfpentafluorophen-yl)arsine gives a 94% yield of tris(pentafluornphenyl)arsme difluoride after reaction with dilute fluorine in fluorotnchloromethane at 0 C [106] Other trivalent arsenic compounds have also been fluorinated with xenon difluoride [103] In addition, arsines have been oxidatively fluorinated by iodine pentafluoride [107] or electrochemically in 26-34% yield [108]... 

When there is an a-hydrogen in the sulfide, the sulfuranes are unstable and cannot be isolated [775]. Sulfoxides [776] and sulfinyl fluorides [777] are oxidatively fluorinated with tluorine to give hexavalent sulfur compounds in yields up to 90%. 

Selective fluonnation in polar solvents has proved commercially successful in the synthesis of 5 fluorouracil and its pyrimidine relatives, an extensive subject that will be discussed in another section Selective fluonnation of enolates [47], enols [48], and silyl enol ethers [49] resulted in preparation of a/phn-fluoro ketones, fieto-diketones, heta-ketoesters, and aldehydes The reactions of fluorine with these functionalities is most probably an addition to the ene followed by elimination of fluonde ion or hydrogen fluoride rather than a simple substitution In a similar vein, selective fluonnation of pyridmes to give 2-fluoropyridines was shown to proceed through pyridine difluondes [50]... 

In quinoline and isoquinoline, the benzene ring is more receptive to fluorma-tion, its double bonds being saturated and the hydrogen atoms replaced in preference to those in the pyridine ring As with pyridine and its homologues, ring contraction takes place during fluorination with cesium tetrafluorocobaltate at... 

Of alicyclic compounds, fluorination of cyclopentane and cyclohexane has been sufficiently investigated in the past. Cycloheptane on fluorination with cobalt trifluoride gives a mixture of highly fluorinated and perfluorinated cycloheptanes and methylcyclohexanes [/2] (equation 12). 

Perfluorodimethyladamantane is prepared from adamantane dicarboxylic acid by treatment with sulfur tetrafluoride followed by energetic fluorination with cobalt trifluoride over two temperature ranges [S] (equation 15)... 

Cesium fluoroxy sulfate [5, dl is prepared by reacting fluorine with cesium sulfate in aqueous solution [20, 21] (equation 3). 

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