Perfluoro Alkyl Hypofluorites and Peroxides Revisited

A more convenient synthesis of the perfluoro alkyl hypofluorite (F(3)C)(3)COF as well as the hitherto unknown (C(2)F(5))(F(3)C)(2)COF compound is reported. Both hypofluorites can be prepared by use of the corresponding tertiary alcohols R(F)OH 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 R(F)OOR(F) [R(F)=(F(3)C)(3)C, (C(2)F(5))(F(3)C)(2)C] 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.