<b>The Chemistry of Carbonyl Fluoride. I. The Fluorination of Organic Compounds</b>

Fawcett, Frank S.; Tullock, C. W.; Coffman, D. D.

doi:10.1021/ja00881a017

Cited by 141 publications

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“…Carbonyl fluoride was prepared in 97% yield by the reaction of carbonyl chloride with sodium fluoride in acetonitrile (7). Carbonyl chloride was a redistilled commercial sample whose purity was checked by infrared examination and molecular weight determination.…”

Section: Carbonyl Fluofidementioning

confidence: 99%

Fully Fluorinated Alkoxides: Part I. Trifluoromethoxides of Alkali Metals

Redwood¹,

Willis²

1965

Can. J. Chem.

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The preparation is described of the trifluoromethoxides of the heavier alkali metals, i.e. MOCF, where M = K, Rb, or Cs. These are stable, crystalline, ionic solids made by the reversible reaction of carbonyl fluoride with the appropriate metal fluoride. No trifluoromethoxides could be prepared from lithium, sodium, barium, or thallium(1) fluorides. Factors affecting the relative stability of such compounds are discussed.Trifluoromethanol, CFBOH, is not known, and is generally assumed to be incapable of existence because of the ease with which compounds having a fluorine atom in a position a to a hydroxyl group would eliminate hydrogen fluoride. Because of this unavailability of the parent alcohol, no metallic trifluoromethoxides have hitherto been reported. We now report the preparation of stable, crystalline trifluoromethoxides of the heavier alkali metals, i.e. MOCF3, where RII = K, Rb, or Cs.A consideration of the possible formation of metallic trifluoromethoxides shows a t once that they are likely to be more ionic in nature than the corresponding methoxides. The completely ionic formulation M+[OCFJd would contain the trifluoromethoxide ion, isoelectronic with the fluoroborate ion, BF4-. The charge in the trifluoromethoxide ion rests formally on the oxygen atom, but it would be shared to some extent by the three fluorine atoms because of their greater electronegativity. The distribution of charge over the whole ion achieved in this way should therefore stabilize it, in a manner not possible in the ionic non-fluorinated methoxides of the alkali metals. The stability of a solid ionic trifluoromethoxide would clearly be influenced by the nature of the cation present, since smaller cations, or those with a high ratio of charge to size, would cause greater polarization of the anion and a correspondingly greater tendency towards decomposition to give a fluoride ion and carbonyl fluoride. In other words, the equilibrium:would be displaced to the left by the presence of large cations. An immediate corollary of this suggestion is that by approaching the equilibrium from the direction of formation rather than decomposition one would have available a possible synthetic route to trifluoromethoxides.

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Section: Carbonyl Fluofidementioning

confidence: 99%

Fully Fluorinated Alkoxides: Part I. Trifluoromethoxides of Alkali Metals

Redwood¹,

Willis²

1965

Can. J. Chem.

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“…CF 3 C(O)F was obtained from Fluorochem (99.5% purity). The preparation and treatment of C(O)F 2 has been described previously [10,20]. HC(O)F was produced according to the method described by Morgan et al [21].…”

mentioning

confidence: 99%

The fluorine atom initiated oxidation of CF3CFH2 (HFC-134a) studied by FTIR spectroscopy

Hasson¹,

Moore²,

Smith³

1998

Int. J. Chem. Kinet.

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Experiments have been carried out on the oxidation of CF 3 CFH 2 (HFC-134a). Reaction was initiated by continuous photolysis of F 2 in the near-ultraviolet. The F atoms produced abstracted a hydrogen atom from CF 3 CFH 2 initiating oxidation in gas mixtures containing O 2 and made up to a total pressure of with N 2 . Product yields were measured 700 torr using Fourier-transform infrared (FTIR) spectroscopy. Experiments were performed with several different partial pressures of O 2 present, and at three temperatures; 298, 323, and 357 K.

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“…""'2d at perhaps even hi~~er temp~ratures (up to ~~1·, the de- The reaction of chromyl chloride and chlorine monofluoride is straight fon·iard, but the other preparations are preferred due to the possibility of fanning chromyl chloride fluoride (Cr0 2 ClF) as a contarni nJn t u~l e ss one i 5 certain e1:?1s ClF 's used. 29 The mechanisns proposed for the reactions of carbonyl fluoride and chlorine monofluoride 1~ith chromiu~ trioxide are based solely on the previously reported reactivity of these reagents as 1·1ell as attempts to expl ain the formation of products observed . Unfortunately, there was no 1·1ay to verify the mechanism through the use of a mass ba 1 ance of components.…”

Section: Reaction Of Cr0mentioning

confidence: 99%

The chemistry of chromium (VI) and chromium (V) oxide fluorides

Green¹

2000

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The Chemistry of Carbonyl Fluoride. I. The Fluorination of Organic Compounds

Cited by 141 publications

References 0 publications

Fully Fluorinated Alkoxides: Part I. Trifluoromethoxides of Alkali Metals

Fully Fluorinated Alkoxides: Part I. Trifluoromethoxides of Alkali Metals

The fluorine atom initiated oxidation of CF3CFH2 (HFC-134a) studied by FTIR spectroscopy

The chemistry of chromium (VI) and chromium (V) oxide fluorides

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