Chlorine monofluorides

Chlorine Monofluoride. Chlorine monofluoride is a colorless gas that condenses to a Hquid with a slight yeUow cast and free2es to a white soHd. The infrared spectmm of gaseous chlorine monofluoride and the Raman spectmm of the Hquid have been studied (36). The uv-absorption spectmm (37) and vapor pressure data are also available (11). 

An equiHbrium exists between chlorine trifluoride, chlorine monofluoride, and fluorine gas (38). The equiHbrium constant may be expressed as... 

Chlorine Trifluoride. Chlorine trifluoride is produced commercially by the continuous gas-phase reaction of fluorine and chlorine ia a nickel reactor at ca 290°C. The ratio of fluorine to chlorine is maintained slightly in excess of 3 1 to promote conversion of the chlorine monofluoride to chlorine trifluoride. Sufficient time ia the reactor must be provided to maintain high conversions to chlorine trifluoride. Temperature control is also critical because the equiHbrium shift of chlorine trifluoride to chlorine monofluoride and fluorine is significant at elevated temperatures. 

The effect of the substituent group can be seen in the reactions of the following senes of halogenated esters Methyl 2,3 dichloro-3-fluoro-2-methylpropionate and chlorine monofluoride first form methyl 2-chloro-3,3-difluoro-2-methylpro-pionate An additional equivalent of chlorine monofluoride produces methyl 2 methyl-2,3,3-trifluoropropionate (equation 14)... 

However, methyl 2,2,3-trichloropropionate and chlorine monofluoride form methyl 2,3 diehloro-2-fluoropropionate An additional equivalent of chlorine monofluoride selectively generates methyl 3-chloro-2,2-difluoropropionate [7i] (equation 15)... 

Chlorine monofluoride can be tamed by reacting it with cyanunc fluoride to form the trimer (CF2NC1)3 The trimer reacts with 1,1-dichloro 2,2,2 tri fluoroethanesulfenyl chloride to form a mixture of 1 chloro-l,2,2,2-tetra-fluoroethanesulfenyl chlonde and perfluoroethanesulfenyl chloride In the same Way, tnfluoroacetyl bromide yields trifluoroacetyl fluonde[14] (equation 16)... 

Chlorine monofluoride m a hydrogen fluoride solution reacts rapidly at low temperature with haloacetate and halopropanoate esters to give 61-80% yields of a a difluoroalkyl ethers [242] (equation 128)... 

C03-0008. Write chemical formulas for the following compounds chlorine monofluoride, xenon trioxide, hydrogen bromide, silicon tetrachloride, sulfur dioxide, and hydrogen peroxide. 

Chlorine-hydrogen hazards, 9 646 Chlorine Institute, 21 831 25 343 Chlorine market, in vinyl chloride manufacture, 25 646 Chlorine monofluoride, 13 123-124 Chlorine monoxide, 8 545t Chlorine oxygen acids/salts, 17 389t Chlorine pentafluoride, 13 125 Chlorine peroxide, oxidation state and stability, 8 545t... 

Photoionization of difluorine and chlorine monofluoride appeared to give an even lower value (68), but a reexamination showed that one of the dissociation processes had been ignored (29). In this method fluorine is exposed to monochromatic UV radiation, and the positive and negative ions are observed in a mass spectrometer. 

Chlorine monofluoride combines smoothly with thiocarbonyl compounds. For instance, the sulfenyl chlorides of the series CFnClg-n-SCl (w= 1, 2, 3), which were already prepared by other methods, are obtained in good yield ... 

Chlorine trifluoride is obtained by heating chlorine or chlorine monofluoride with fluorine ... 

Hypochlorous acid also may be obtained by hydrolysis of chlorine monofluoride ... 

Chlorine monofluoride oxide, 18 328-330 force field of, 18 329, 330 infrared spectrum of, 18 328, 329 stretching force constants for, 18 330 synthesis of, 18 328 Chlorine nitrate fluorination of, 18 332 preparation of, 5 54 Chlorine oxides, 46 109-110, 158 fluorination of, 18 348 Chlorine oxyfluorides, 18 319-389, see also specific compounds adduct formation, 18 327, 328 amphoteric nature of, 18 327, 328 bond lengths, 18 326 bond strengths, 18 323-327 geometry of, 18 320-323 ligand distribution, 18 323 reactivity of, 18 327, 328 stretching force constants, 18 324-327 Chlorine pentafluoride oxide, 18 345, 346 Chlorine trifluoride, reaction with difluoramine, 33 157... 

Chlorine monofluoride can be prepared from elemental chlorine and fluorine at 400 C or, better, from (i) commercially available chlorine trifluoride and chlorine at 180°C,19 (ii) chlorine trifluoride and chlorine in the presence of cesium fluoride, or (iii) chlorine trifluoride and rner-cury(II) chloride at 25 C.20... 

The reaction of perfluorovinylamines with chlorine monofluoride results in bidirectional addition to form a mixture of isomers, e.g. 1 and 2 (1/2 = 69 31) in 95% yield.25... 

The stoichiometric equivalents of halogen fluorides, i.e. chlorine monofluoride, bromine monofluoride and iodine monofluoride, have found a wide application in addition reactions to double bonds. The equivalents are obtained by reacting A -haloamides or free halogens in combination with hydrogen fluoride or its salts as the source of fluoride ions. The reactions proceed under mild conditions at — 80 to 20 "C in anhydrous hydrofluoric acid or diethyl ether, tetrahydro-furan, dichloromethane or chloroform mainly by electrophilic addition with Markovnikov-type regioselectivity (anti addition).26-28... 

Boron trifluoride and boron trifluoride-diethyl ether complex can be used as a source of fluoride ions in the presence of hypobromites and hypochlorites, e.g. methyl hypobromitc, tert-butyl hypobromite, methyl hypochlorite in carbon tetrachloride at 25 C. The addition of bromine monofluoride" and chlorine monofluoride" to various alkenes is accompanied by the formation of the corresponding alkoxybromides and alkoxychlorides which hinder the isolation of the halofluorinated products.57 jV-Bromo- and A -chloro-substiluted alkyl- and arylamines. -amides, and -imides, A -chloro-A,-methylamine, A -bromo-A -methylamine, A -chloro-A, /V-dimethylamine, A-bromo-A.A-dimethylamine, ACV-dichloro-A -methylamine, V,fV-dibromo-,V-mcthylaminc, A -bromosuccinimide, -V-chlorosuccinimide, Af-bromoacct-amide, A.A -dichlorourethane, can be used in the reaction instead of the hypohalites. The reactions with various alkenes conducted in dichloromethane at room temperature in the presence of boron trifluoride-diethyl ether complex produce bromofluoro and chlorofluoro addition products in 40-80 % yield. However, the reactions are complicated by the addition of A -halo-succinimides and Af.A-dichlorourcthane to the C = C bonds.58... 

Addition of Chlorine Monofluoride to Multiple Heteroatomic Bonds... 

The reactions catalyzed by Lewis acids are conducted for 10-20 hours at — 20 C to give hypochlorites in almost quantitative yield.82 Chlorine monofluoride activated by hydrogen fluoride to enhance its electrophilicity transforms the carbonyl function in esters of carboxylic acids to a difluoromethyl group. The reactions are carried out by passing 2molar equivalents of chlorine monofluoride gas through a solution of the ester in an equal volume of hydrogen fluoride at - 70 to - 30°C.83... 

The addition of chlorine monofluoride to perhalothiocarbonyl compounds produces the corresponding sulfenyl chlorides.84... 

The thiocarbonyl carbon in the substrates involved can carry not only chlorine atoms or tri-fluoromethylsulfanyl groups but also fluoro, bromo, and isothiocyanato substituents. In the last case, the addition of chlorine monofluoride across the C = S bond affords the sulfenyl chlorides in 20-35% yield.84... 

Chlorine monofluoride adds quantiatively to C = N bonds to give IV-chloro derivatives.85... 

When treated with chlorine monofluoride, perhalohydrazones are converted into hydrazines in high yield.86... 

Trifluoromethyl, fluoroformyl, and trifluoroacetyl isocyanates87 as well as A-haloimines88 easily add chlorine monofluoride to the C = N bonds. 

The low-temperature addition of chlorine monofluoride to fluorinated nitriles is a general method for preparing fluorinated aliphatic dichloroamines in 65-75% yield.89... 

When treated with stoichiometric equivalents of chlorine monofluoride and bromine monofluoride at 0 to 25°C, perfluorobenzonitrile affords perfluoro-NW-dichlorobenzylamine and perfluoro-AW-dibromobenzylamine in 60 and 37% yield, respectively.91... 

Chlorine monofluoride converts polyfluoroalkyl chlorosulfites into the corresponding fluorosul-fites apparently through addition to the S = 0 bond and subsequent elimination of chlorine.92... 

Polyfluoroalkyl fluorosulfates are formed on reacting dialkyl sulfites with chlorine monofluoride, presumably via an Arbuzov rearrangement.93... 

When exposed to chlorine monofluoride at — 78 CC, A4 S = N bonds undergo cleavage to form > SF2 and —NC12 compounds,94 but A6 S = N bonds readily add chlorine monofluoride at 50 C or, in the presence of cesium fluoride, at 25 "C without fragmentation.95... 

Chlorine monofluoride is capable of oxidizing a sulfur atom bonded to one or two perfluoroalkyl groups through the addition of two or four fluorine atoms to the sulfur atom, depending on the ratio of the reagents and the reaction temperature. 

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