Brehm, Oliver:

Untersuchungen zur Einführung der polyfluorierten Gruppen CF 3 (CF 2)5 -C 2 H 4 und C 6 F 5 in Alkyl- und Arylchlorsilane

(2004), 140 Bl.
Dissertation / Fach: Chemie
Duisburg, Essen, Univ., Diss., 2004
Abstract:
This thesis describes the syntheses of the silanes, Bis(1H,1H,2H,2H-tridecafluorooctyl)dichlorosilane, Tris(1H,1H,2H,2H-tridecafluorooctyl)chlorosilane and Tetrakis(1H,1H,2H,2H-tridecafluorooctyl)silane. The Polyfluorooctylchlorosilanes were obtained by the reaction of Phenylchlorosilanes with stoichiometric amounts of Tridecafluorooctyllithium in Ether at -40 °C to give the Phenyl(tridecafluorooctyl)silanes, which were further reacted with Aluminiumtrichloride in Dichloromethane. Tetrakis(1H,1H,2H,2H-tridecafluorooctyl)silane has been synthesized by reaction of Tridecafluorooctyllithium with Tetrachlorosilane in Ether at -40 °C. Systematic investigations on the reactivity of Alkyl- and Arylchlorosilanes towards nucleophilic reactants, such as C6F13C2H4MgBr, C6F13C2H4MgI, C6F5MgBr and C6F5MgI were undertaken. Within these investigations we have shown that Tridecafluorooctylmagnesium bromide is suitable to introduce a long-chain fluoroorganyl group into Bis(pentafluorphenyl)dichlorosilane forming the tetravalent Bis(pentafluorophenyl)bis(tridecafluorooctyl)silane. No reaction occurred when changing the strongly electron withdrawing pentafluorophenyl group with its proton analoque, which likely arises from electronic but not from steric aspects. The complete assignments of the 19F- and 13C-NMR spectra of Tridecafluorooctyliodide as well as of several Tridecafluorooctylsilanes were solved using combinations of 1D and 2D NMR experiments.