Hexafluoroacetone-Hydrogen peroxide

The epoxides (81) themselves have been synthesized by treatment of 4,7-dihydro-1,3-dioxepins (77) withp-nitro- <75BSF1763> or w-chloroperbenzoic acid <75TL2643> or HOCI/H2O2 <8IEUP33426). Alternatively, hexafluoroacetone/hydrogen peroxide in disodium hydrogen phosphate buffered... 

Hexafluoroacetone and hydrogen peroxide in buffered aqueous solution can epoxidize alkenes and allylic alcohols.101 N, Af-Dialkylpiperidin-4-one salts are also good catalysts for epoxidation.102 The polar effect of the quaternary nitrogen enhances the... 

Anderson, L. R. et al., J. Fluorine Chem., 1976, 7, 481-500 Five derivatives, including the 0-0 lithium or sodium salts of the hydrogen peroxide adduct of hexafluoroacetone (2-hydroxyhexafluoro-2-propyl hydroperoxide), and their reaction products with acyl halides, are less flammable or explosive than their hydrocarbon analogues, though less stable than the parent hydroperoxides. Relevant entries are ... 

M. C. A. van Vliet, I. W. C. E. Arends, R. A. Sheldon, Hexafluoroacetone in hexafluoro-2-propanol A highly active medium for epoxidation with aqueous hydrogen peroxide, Synlett (2001) 1305. 

Oxidation. Hexafluoroacetone (available from Aldrich) and hydrogen peroxide form a complex which functions as a peracid. Thus it can be used in the Baeyer-Villiger reaction and for oxidation of a primary aromatic amine to a nitro compound. Preliminary results, however, indicate that the adduct is less powerful than pertrifluoroacetic acid.1... 

Oxirans.— Epoxides are readily available from the catalytic oxidation of alkenes with 2-hydroperoxyhexafluoropropan-2-ol (HPHI) (1), which itself is easily prepared from hexafluoroacetone hydrate (2) and hydrogen peroxide (Scheme 1). HPHI is claimed to have similarities to the natural flavin hydroperoxides which are implicated in epoxidations and hydroxylations by external flavoprotein mono-oxygenases. Yields are typically in the range 77—92%. 

Hydroperoxyhexafluoro-2-propanol has been reported to oxidize aldehydes to carboxylic acids efficiently, while alcohol groups and isolated double bonds are not attacked.The reagent is simply prepared from hydrogen peroxide and hexafluoroacetone the latter can be used in stoicheiometric or catalytic quantities. 

Similarly, the adduct of hydrogen peroxide with hexafluoroacetone is an active epoxidizing reagent. ... 

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