- Perfluoro Alkyl Hypofluorites and Peroxides Revisited
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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.
- Nissen, Jan H.,Drews, Thomas,Schr?der, Benjamin,Beckers, Helmut,Steinhauer, Simon,Riedel, Sebastian
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- No Fear of Perfluorinated Peroxides: Syntheses and Solid-State Structures of Surprisingly Inert Perfluoroalkyl Peroxides
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We report on the solid-state structures of bis(nonafluoro-tert-butyl) peroxide [(F3C)3CO]2 and bis(undecafluoro-2-methyl-2-butyl) peroxide [(C2F5)(F3C)2CO]2. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid-state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O?O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X2). Ferrocene is oxidized by [(F3C)3CO]2 to [FeIIICp2][OC(CF3)3].
- Nissen, Jan H.,Stüker, Tony,Drews, Thomas,Steinhauer, Simon,Beckers, Helmut,Riedel, Sebastian
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- Organic compounds bearing a difluoroaminooxy group
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A preparative method for the synthesis of C-and N-difluoroaminooxy compounds was elaborated. The method involves the reaction of N,N-difluoro-O-fluorosulfonyl hydroxylamine with the corresponding alkoxides and N-oximide salts. It was shown that N-difluoroaminooxy compounds can add to olefins at the double bond.
- Fokin,Studnev,Stolyarov,Valiev, R.Sh.
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- From hypochlorites to perfluorinated dialkyl peroxides
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The synthesis and characterization of the new perfluorinated hypochlorite, undecafluoro-tert-pentyl hypochlorite, (C2F5)(F3C)2COCl, is reported. Its gas-phase infrared, UV/Vis and NMR spectra have been recorded and its spectroscopic properties are discussed and compared with quantum-chemical predictions and those of other known perfluorinated hypochlorites such as RFOCl [RF = F3C, (F3C)3C, (C2F5)(F3C)2C]. A synthetic route to otherwise difficult to access perfluorinated dialkyl peroxides, RFOORF, is also provided by low-temperature photolysis of the corresponding hypochlorite.
- Nissen, Jan H.,Wickemeyer, Lucas,Stüker, Tony,Steinhauer, Simon,Beckers, Helmut,Riedel, Sebastian
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supporting information
(2019/12/26)
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- PROCESS FOR THE PREPARATION OF FLUORINATED PEROXIDES
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The present invention relates to the preparation of perfluorinated or partially fluorinated peroxides which avoids the use of carbonyl fluoride (COF2).
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Page/Page column 8
(2019/11/12)
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