Perfluoroalkyl Peroxides, Trioxides, and Hypohalites

Perfluoroalkyl Peroxides, Trioxides, and Hypohalites. U.v. irradiation of a gaseous mixture of hexafluoroacetone, fluorine, and oxygen has been shown to give bistrifluoromethyl trioxide in 60% yield substitution of perfluoro-cyclobutanone for hexafluoroacetone leads to the formation of fluoroformyl trifluoromethyl peroxide (35%) as well as the trioxide (35%). Treatment 

The results of a study of the kinetics of the thermal reaction between nitric oxide and bistrifluoromethyl peroxide (proposed overall stoicheiometry 2NO + CF3 O O CF3 - 2NOF 4- 2COF2) have been presented. They are in good agreement with the independent work of Heicklen and Knight reported in 1967.  

The new fluorocarbon peroxides (CFslgC O O QCFgjg and (CFg) -(C2F5)C O O C(C2F5)(CFj)8 have been prepared by oxidation of the corresponding perfluorinated tertiary alcohols with chlorine trifluoride they are stable at room temperature for indefinite periods, and the former boils at 99 °C with only slight decomposition.  

Studies on the well known reaction between fluorine and carbon monoxide have revealed that a film of silver fluoride(s) on copper truly is a catalyst for the reaction Fj + CO - COFa, and for subsequent changes producing bistrifluoromethyl peroxide and trifluoromethyl hypofluorite, whereas caesium fluoride is not and since neither copper nor silver iluoride(s) appears to be a good catalyst for the reaction CF3 OF + COFj CFa O O CFg, it has been suggested that the fluorination of carbon monoxide or carbonyl fluoride in the presence of silver difluoride may possibly involve the steps 

Trifluoromethyl hypofluorite has been shown to be the major product of the reaction between caesium trifluoromethoxide and CFa(OF)g (see above), and also to occur in the products from the electrochemical fluorination of phosgene (ca. 7% yield) and A/-fluoroformyliminosulphur difluoride.  

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