- Fluorination of propane and propene over cobalt(III) trifluoride and potassium tetrafluorocobaltate(III)
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Fluorination of propane and propene over cobalt(III) fluoride and potassium tetrafluorocobaltate(III) gave complex mixtures of products which have been identified to the 0.5percent level.The reactions are valuelles for preparative purposes.The mechanism of the fluorinations is not a simple F-for-H replacement, but requires an initial conversion of propane into propene followed by carbocation- and radical mediated reactions: the carbocations can be quenched by fluoride ions, rearrange and eliminate, and the radicals can be oxidised to carbocations or quenched by fluorine atoms.Radical quenching tends to predominate late in the fluoronation and carbocation reactions at the beginning.
- Burdon, James,Garnier, Laurent,Powell, Richard L.
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p. 625 - 632
(2007/10/03)
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- Reductive dehalogenation of polyhalofluorocarbons with tributyltin hydride
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The reduction of polyhalofluorocarbons, including ClCF2CFClCF2Cl, (ClCF2CFCl)2, ICH2(CF2)3CH2I and vicinal dichloroperfluorocycloalkanes, with tributyltin hydride gave the corresponding hydrofluorocarbons in good to excellent yield.The results are compared with similar reductions with other reducing agents, and to tin hydride reductions of non-fluorinated analogs. - Keywords: Reductive dehalogenation; Polyfluorocarbons; Tributyltin hydride; NMR spectroscopy; Hydrofluorocarbons
- Puy, Michael Van Der,Belter, Randolph K.,Borowski, Ralph J.,Ellis, Lois A. S.,Persichini, Phillip J.,et al.
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- HOMOLYTIC TRANSFORMATIONS OF FLUORINE-CONTAINING ACETALS
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Study of the homolytic transformations which occur during the dissociation of di-tert-butyl peroxide in linear fluorine-containing acetals (derivatives of 2,2,3,3-tetrafluoropropanol and 2,2,3,3,4,4,5,5-octafluoropentanol) shows that the reactivity of the molecule of the fluorine containing acetal is determined mainly by the C-H bonds adjacent to the two oxygen atoms, and the products from the fragmentation of the obtained dialkoxyalkyl radicals are fluorinated esters and alkyl radicals.The abstraction of a hydrogen atom from the molecules of the oligomeric formalsH(CF2)n(OCH2)mOCH2(CF2)nH leads to the dialkoxyalkyl radicals, which undergo fragmentation at the C-H bonds at the β position to the radical center with the formation of oligomeric esters H(CF2)n(OCH2)iOC(O)H (i = 1...m).
- Yakupov, I. S.,Germash, A. V.,Zlotskii, S. S.,Rakhmankulov, D. L.
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p. 1024 - 1028
(2007/10/02)
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