Perfluoro Alkyl Hypofluorites and Peroxides Revisited

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. Once upon a time… Hypofluorites: The convenient synthesis of alkyl hypofluorites RFOF [RF=(F3C)3C, (C2F5)(F3C)2C] is the origin story for perfluoro bisalkyl peroxides. Hypofluorites are prepared from the corresponding alcohols RFOH and elemental fluorine. The perfluoro bis‐tert‐butyl peroxide is highly inert towards oxidizers and even dissolves elemental fluorine without decomposition.