Abstract
A more convenient synthesis of the perfluoro alkyl hypofluorite (F3C)3COF as well as the hitherto unknown (C2F5)(F3C)2COF compound is reported. Both hypofluorites can be prepared by use of the corresponding tertiary alcohols RFOH and elemental fluorine in the presence of CsF. An appropriate access to these highly reactive hypofluorites is crucial. The hypofluorites are then transferred into their corresponding perfluoro bisalkyl peroxides RFOORF [RF=(F3C)3C, (C2F5)(F3C)2C] by treatment with partially fluorinated silver wool. NMR, gas‐phase infrared, and solid‐state Raman spectra of the perfluoro bisalkyl peroxides are presented and their chemical properties are discussed.
Highlights
Cady and Kellogg described the synthesis of the first perfluoro alkyl hypofluorite, trifluoromethyl hypofluorite, F3COF, by the AgF2-catalyzed direct fluorination of methanol in 1948.[1]
We found that perfluoroalkyl hypofluorites RFOF are excellent starting compounds for the synthesis of otherwise difficult to access perfluoro bisalkyl peroxides RFOORF (2),[18] which are synthetically valuable sources of fluoroalkoxy radicals, RFOC.[19]
The number of perfluoroalkyl hypofluorites 1 obtainable by this procedure can be further increased by using perfluoro alkylalcohols 3 instead of the perfluoro carbonyl compounds according to Equation (2)
Summary
Cady and Kellogg described the synthesis of the first perfluoro alkyl hypofluorite, trifluoromethyl hypofluorite, F3COF, by the AgF2-catalyzed direct fluorination of methanol in 1948.[1]. An alternative route to perfluoro alkyl hypofluorites is the fluorination of perfluoro ketones in the presence of metal fluorides, MF (M = K, Rb, Cs) [Eq (1)], as described in 1966 by Ruff et al.[7] the direct fluorination (with 10 % F2 in N2) of sodium trifluoroacetate, F3CCO2Na,[8] or trifluoroacetic acid, F3CCO2H,[9] leads to the formation of hypofluorite compounds in a temperature-dependent ratio. These hypofluorites were used in the pioneering works by Hesse and co-workers[10] and Rozen[11] as electrophilic fluorination agents or as etching gas[12] for semiconductors.
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