Perfluoroacetone

The ethoxycarbonylimme of perfluoroacetone reacts with phosphorus pen-tachlonde under mild condtions This reaction is a convenient synthesis of a-chlo-rohexafluoropropyl isocyanate [73] (equauon 60). 

Molecular ion is usually not observed with perfiuorinated ketones, but may be deduced by adding 19 Daltons to the highest mass observed in the case of perfluoroacetone and 69 Daltons in the case of perfluorodiethyl ketone. A characteristic fragment ion results from a-cleavage ... 

The [2h-2] cycloaddition could occur thermally in the pseudoexcitation band. In fact, an alkyne with electron-donating group, ethoxyacetylene, and electron accepting carbonyl compound, perfluoroacetone, form the oxetene at low temperature (-78 °C) without light irradiation (pseudoexcitation band in Scheme 6) [26, 27],... 

Isomeric products (75) and (76) are obtained from the reaction of perfluoroacetone with dialkyl phosphites. " The relative proportions of the isomeric mixture depend on the alkyl group in the phosphite and the results are explained in terms of the polarity of the P-H bond and hence its direction of addition to the carbonyl group. Presumably, the balance in these cases is very finely adjusted, although these reactions are possibly more complicated than the results suggest. 

In addition, perfluoroacetone reacted with butadiene to give 2,2-bis(trifluoromethyl)-3,6-divinyltetrahydropyrane (112) and 1,1,1-trifluoro-2-trifluoromethyl-3,5-hexadien-2-ol (113). 

Synonyms HFA acetone, hexafluoro per-fluoro-2-propanone perfluoroacetone 1,1,1, 3,3,3 -hexafluoro-2 -propanone... 

Fluorous solvents proved to be highly effective in epoxidation of alkenes. H202 can be used in combination with trifluoroacetone,27 perfluoroacetone,28 or a mixture of perfluoroacetone and hexafluoro-2-propanol.29 In fluorinated alcohols as solvents uncatalyzed epoxidations with aqueous H202 are performed.30,31... 

Finally, branched compounds are prepared from perfluoroacetone. 

Hydroxyalkyl)phosphonic acids, and also the related phosphinic acids, are normally obtained from hydrogen phosphonates and aldehydes or ketones. The reactions between perfluoroacetone and mixed dialkyl hydrogen phosphonates are noteworthy in that the expected products (129) may be accompanied by the phosphoric triesters (130). Trimethylsilyl alkylene P(III) triesters (131) are also useful starting materials when acted upon by aromatic aldehydes or by (1-oxoalkyl)phosphonic acid esters, the initial... 

Dialkyl trimethylsilyl phosphites and perfluoroacetone react together to yield one, or more, of the products (9), (10)... 

Epoxidations. In the presence of perfluoroacetone and (V-hydroxyphthalimide, hydrogen peroxide generated in situ from oxygen and 1-phenylethanol epoxidizes alkenes without a metal catalyst, although there is also an alternative in using N-hydroxyphthalimide, Mo(CO)e, and Co(OAc)2. 

A recent study on the rate of formation of products from excited hexafluoro-acetone in the presence of a vibrational relaxer and azoalkanes as triplet quenchers has produced data which the authors use to support the notion that vibrational relaxation in the singlet manifold is a multistep collisional process.75 76 The reaction between excited perfluoroacetone and ethane78 and the photochemistry of hexafluorobiacetyl vapour77 have also been discussed. 

Although it has been stated that di- and tri-haloketones and a-haloaldehydes (irrespective of the degree of halogen substitution) tend to yield only enol phosphate esters, further qualification of this statement is appropriate. The formation of silyl ethers from aldehydes or ketones and silyl phosphites has already been noted (see section III.A). Reactions between silyl phosphites and trifluoroacetaldehyde or perfluoroacetone and other similar compounds initially lead to silyl ethers of (a-hydroxyalkyl)phosphonic diesters in which all the fluorine is retained, although subsequent change leads to fluorinated enol phosphate esters. Sekine et also observed the formation of (a-silyloxyalkyl)phospho-... 

Synonyms/Trade Names Hexafluoro-2-propanone 1,1,1,3,3,3-Hexafluoro-2-propanone HFA Perfluoroacetone ... 

Scheme 1. Trapping of TpRe(O) by dioxygen ( 0 = 0) and reaction of complex 1 with perfluoroacetone in the presence of dioxygen.

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