A study of the bromination of saturated organic compounds
Schiller, James C.
Doctor of Philosophy
Before the work was carried out, which is reported on in detail in the next section, a series of preliminary experiments was performed. These were designed to show the effects of various physical and chemical agents on the speed of the bromination and the configuration of the products. It was found that the addition of almost any solid to the hydrocarbon to be brominated very greatly increased the time necessary for the bromination to take place. This was true with iodine, anhydrous AlCl3, powdered sulphur, and powdered glass. The use of benzoyl peroxide and myristoyl peroxide as catalysts were failures in that these materials also slowed down the rate of substitution. All of these instances are probably examples of the breaking of the chain reaction of bromination. Inert liquid foreign materials, such as nitrobenzene and ethyl acetate, also slowed down the reaction, probably for the same reason. Only two factors were noticed which would materially speed up the bromination. First, the presence of small amounts of water very greatly reduced the time required for bromination, but when the products were distilled it was found that they consisted very largely of polysubstituted derivatives. This is in line with the findings of several earlier investigators. Secondly, as to be expected, it was found that intense activation of the reactants by light, greatly increased the speed of the reaction. It was hoped that a definite contribution could be made to the knowledge of paraffin bromination.