THE FUNCTIONALIZATION OF SATURATED-HYDROCARBONS .23. GIF-TYPE BROMINATION AND CHLORINATION OF SATURATED-HYDROCARBONS - A NONRADICAL REACTION

The bromination of saturated hydrocarbons was studied in the GoAgg(III) system using CBrCl3 and other polyhaloalkanes. This bromination reaction was compared to free radical processes by (i) evaluating the rates of reactions for a series of polyhaloalkanes, by (ii) measuring the selectivity of the different systems towards various saturated hydrocarbons and by (iii) analyzing the product distribution arising from the bromination of cyclohexyl bromide under both the GoAgg(III) type conditions and from known processes for alkyl radical generation. Some chlorine containing reagents were also examined for C-Cl bond formation in the GoAgg(III) system. All the experimental findings support a mechanism for the reaction that is different from one involving free radicals. This non-radical pathway is common in all Gif-type systems, as seen in common patterns of selectivity.