The Effect of Mercury on the Quantitative Bromination of Unsaturated Compounds

It has been shown that the simple bromide, bromate procedure for the determination of unsaturation is unsatisfactory for triple bonded compounds. Davis, Crandall and Hibee (1) have pointed out that in the case of acetylene, interference is due to the presence of oxygen. Quantitative bromination can be achieved by carrying out the reaction ·n an oxygen free system (evacuated). The authors / also pointed out that the bromination of acetylene is catalysed by aluminum, nickel and mercury salts. Frieman, Kennedy and Lucas (2) have definitely shown that the use of a mercuric sulfate catalyst in the bromination of a sulfuric acid solution of acetylene yields theoretical results, each mole of acetylene adding two moles of bromine. Mulliken and Wakeman (3) attempted to determine liquid alkynes by bromination and obtained low results. The purpose of the work presented in this thesis is to find a general method f or the quantitative bromination of unsaturated compounds by studying: (a) The bromination of different triple bonded compounds. (b) The effect of mercuric sulfate on these brominations. (c) The effect of mercury upon the bromination of double bonded compounds, both those easily and those difficultly brominated in the absence of mercury. (d) The effect of 1 oxygen and peroxides on these systems.