ChemInform Abstract: SALZE VON DIARYLJODONIUMDIFLUORIDEN

Abstract

Die Diaryljodosyltrifluoracetate (I) gehen unter der Einwirkung von SF4 in Methylenchlorid bei ‐10 bis 0°C in die Difluoride (II) (Ausbeute 78 bzw. 65%) über.

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

“…The precipitation of products, R F IF 2 , protects them against further fluorination to R F IF 4 . The direct chlorination of perfluoroalkyl iodides to R F ICl 2 was not successful [12]. At this point we should remember that R F I molecules have a partial positive charge on iodine in common.…”

“…The oxidation can be performed with ozone [35], HNO 3 [36], or a peroxoacid [12,37,38]. These reactions (Eqs.…”

“…In principle R F IX 2 and R F IX 4 molecules can be transformed into the corresponding oxo derivatives R F IO (C 6 F 5 IO [12,36,40,105]; CF 3 IO [35]), R F IOF 2 (CF 3 IOF 2 [35], C 6 F 5 IOF 2 [107]), and R F IO 2 (CF 3 IO 2 [35], C 6 F 5 IO 2 [107]. In aqueous media, this conversion can be considered as an equilibrium reaction with acidic HX as coproduct.…”

“…The latter can be converted into the corresponding halides [37,55]. Pentafluorophenyliodonium salts were obtained analogously (Eq.…”

Selective Oxidation of Alkanes and Ethers with Iodine Tris(trifluoroacetate)

“…Whether the attacking species is ( I ) , I(OAcf)?, or even IOAcf has not been established. Derivatives of (dihydroxyiodo)alkanes, e. g. (6), are unstable (unless the alkyl group is perfluorinated[61) and undergo 1,l-elimination to give alkyl trifluoroacetates, e. g. (2), or 1,2-elimination affording an alkene which is oxidized stereoselectively to alkylene bis(trifluoroacetates), e.g. (3)"l. The observation that 2-iodobutane gives the same products as butane on treatment with ( 1 ) suggests that the reaction proceeds via bis(trifluor0-acetoxy)iodoalkanes ( 6 ) .…”