353-50-4 carbonyl difluoride

Carbonyl difluoride is not an esoteric material simple methods for its synthesis are well documented, and patents describing its economic preparation on a commercial scale are 

It is notable that the chemistry and properties of COF can be summarized in one chapter, whereas twelve chapters were required to describe the chemistry and properties of phosgene. However, examination of this chapter reveals that, if anything, the chemistry of COFj is even more interesting, and potentially more wide-ranging, than that of phosgene. We fervently hope that this chapter will rekindle interest in this much neglected molecule. 

The structure of this chapter mirrors the ordering of material in Section A. 

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An example of cleavage ol the sulfur-oxygen bond in trifluoromethane-sulfonic ester has been reported Tnfluororaethyl triflate reacts with neutral or anionic nucleophiles with elimination of carbonyl difluoride and formation of trifluoromethanesulfonyl fluoride [57] (equation 32) The mechanism of this reaction involves elimination of fluoride ion, which is a chain carrier in the substitution of fluorine for the trifluoromethoxy group... 

Sodium nitrite in dimethylformamide acts as a nucleophile and reacts with perfluoropropene to generate a perfluoroalkyl nitrite anion The intermediate carbanion undergoes intramolecular nitrosation with loss of carbonyl difluoride to give tnfluoroacetic acid upon hydrolysis [5] (equation 6)... 

Synonyms carbon oxyfluoride carbonyl difluoride fluoroformyl fluoride flu-orophosgene... 

In the area of reaction energetics. Baker, Muir, and Andzehn have compared six levels of theory for the enthalpies of forward activation and reaction for 12 organic reactions the unimolecular rearrangements vinyl alcohol -> acetaldehyde, cyclobutene -> s-trans butadiene, s-cis butadiene s-trans butadiene, and cyclopropyl radical allyl radical the unimolecular decompositions tetrazine -> 2HCN -F N2 and trifluoromethanol -> carbonyl difluoride -F HF the bimolecular condensation reactions butadiene -F ethylene -> cyclohexene (the Diels-Alder reaction), methyl radical -F ethylene -> propyl radical, and methyl radical -F formaldehyde -> ethoxyl radical and the bimolecular exchange reactions FO -F H2 FOH -F H, HO -F H2 H2O -F H, and H -F acetylene H2 -F HC2. Their results are summarized in Table 8.3 (Reaction Set 1). One feature noted by these authors is... 

Both aromatic and aliphatic fluoroformates 7 can be readily prepared from phenols or alcohols and carbonyl difluoride and treated with sulfur tetrafluoride without isolation. Hydrogen fluoride evolved in the reaction of hydroxy compounds with carbonyl di fluoride serves as a catalyst for the consecutive reaction with sulfur tetrafluoride.15<)-162 This provides a general, convenient, direct synthesis of aryl and alkyl trifluoromethyl ethers 5 from phenols and alcohols. When the intermediate fluoroformate 7 is isolated prior to treatment with sulfur tetrafluoride, at least one mole equivalent of hydrogen fluoride is necessary to promote the fluorination reaction. 159 163 Representative examples of the conversion of hydroxy compounds 6 into trifluoromethyl ethers 5 via intermediate fluoroformates 7 are given (for other examples 7 -> 5, see Houben-Weyl, Vol. E4, pp 628. 629). 

Urea, melamine, cyanamide, dicyandiamide, and guanidine react at elevated temperatures with sulfur tetrafluoride to give (trifluoromethyl)iminosulfur difluoride (7) in 6-25% yield.172 In the presence of sodium fluoride at 25"C, urea is converted into fluorocarbonyliminosulfur difluoride (8), but at 50°C thiazyl fluoride (9) is the main product, both formed in ca. 60% yield. At higher temperatures, carbonyl difluoride (carbonic difluoride) and sulfur hexafluoride are the sole products of the reaction of urea with sulfur tetrafluoride.173... 

Carbonyl difluoride (2) has been used to convert the carbonyl group in ketones, aldehydes and amides to the corresponding difluoromethylene group. 

The fluorination involves two distinct steps, the first is the addition of carbonyl difluoride to the carbonyl group to give an intermediate, e.g. 4, which can be isolated, and the second is... 

However, hexafluoroacetone is broken down almost completely87 over potassium tetrafluoro-cobaltate(III) at 250°C only traces of trifluoroacetyl fluoride are detected, the rest being carbon tetrafluoride and carbonyl difluoride. This shows that even if perfluoro ketones are formed in fluorination processes, they will break down, thus demonstrating that transition metal fluoride fluorination will not produce polyfluoro ketones. 

Carbonyl-bis(triphenylphosphine)iridium—silver diperchlorate, 3892 Carbonyl dicyanide, see Oxopropanedinitrile, 1337 Carbonyl difluoride, 0342a Carbonyl diisothiocyanate, 1338 Carbonyl(pentasulfur pentanitrido)molybdenum, 0532 2-Carboxy-3,6-dimethylbenzenediazonium chloride, 3132a Carboxymethyl carbamimoniothioate chloride,... 

Trimethylsilylamino tellurium pentafluoride treated with carbonyl difluoride at 60° produced carbonylamino tellurium pentafluoride7 . 

Carbonylamino Tellurium Pentafluoride3 3.1 g (10 mmol) of trimethylsilylamino tellurium pentafluoride are placed in a 100 ml stainless steel cylinder which is then cooled. 1.98 g (30 mmol) of carbonyl difluoride are condensed into the cylinder which is then closed and heated at 60° for 15 h. The resultant mixture is distilled under a dynamic vacuum through —78° and —196° traps. The contents of the —196° trap are pumped... 

Carbonyl difluoride, COF,. Pungent hygroscopii. gas. Preparation. Supplier PCR Research Chemicals. 

FLUORINATION Acetyl hypofluorite. Carbonyl difluoride. N-Fluoro-N-alkyl-p-tolu-enesulfonamides. 

Carbonyl difluoride, COF2. Pungent hygroscopic gas. Preparation.1 Supplier PCR Research Chemicals. 

The reaction of amides with sulfur tetrafluoride or with carbonyl difluoride leads to fluorinated compounds with a nitrogen substituent at the difluoromethylene or trifluoromcthyl group and thus these reactions are not covered here. 

Oxygen difluoride reacts rapidly with selected alkenes at low temperatures however, per-fliioroalkenes are less reactive than the corresponding alkylalkenes and require either thermal or ultraviolet activation." The oxidation, which is a homogeneous chain reaction," of hexa-fluoropropene, tetrafluorocyclopropene, and pcrfluorobut-2-ene all give a variety of products such as carbon tetrafluoridc, carbonyl difluoride, hexafluoroethane, oxiranes, and other oxidation products." This reaction is not useful for preparative organic work. 

The smallest carbon oxyfluoride, carbonyl difluoride, COF2, can be synthesized from phosgene by metathesis with... 

The electrophihc nature of COF2 is beneficial in the reaction of carbonyl difluoride with CsF, which produces trifluoromethyl hypofluorite (CF3OF) with fluorine and triflnoromethyl hypochlorite (CF3OCI) with chlorine monoflnoride. Both reactions imply the presence of the triflnoromethoxide anion as an intermediate. 

Trifluoromethyl hypofluorite can be reacted with carbonyl difluoride to yieldbis(trifluoromethyl) peroxide, CF3OOCF3, a colorless gas, bp -37 °C, which is quite stable up to 220 °C and chemically relatively inert (equation 53). At high temperatures the peroxide appears to be in equilibrium with COF2 and CF3OF. The peroxide is best prepared by reaction of CO and F2 over AgF2 at 220 °C (equation 54). 

Bis(fluoroxy)difluoromethane reacts with carbonyl difluoride over CsF to yield a bis(trifluoromethyl) trioxide, CF3OOOCF3, bp -19°C, or the peroxy acyl fluoride, CF300C(0)F, depending on conditions (equation 55). At low temperature, the trioxide is favored. 

Fluorine and trifluoromethyl groups appear to stabilize oxygen catenation. The trioxide can be approached alternatively by the reaction of oxygen difluoride and carbonyl difluoride over a metal fluoride catalyst. Depending on conditions, the trioxide will be the major product (equations 56 and 57). 

SYNS CARBON DIFLUORIDE OXIDE CARBON FLUORIDE OXIDE CARBONIC DIFLUORIDE CARBON OXYFLUORIDE CARBONYL DIFLUORIDE DIFLUOROFORMALDEHYDE FLUOPHOSGENE FLUOROFORMYL FLUORIDE FLUOROPHOSGENE RCRA WASTE NUMBER U033... 

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