Free radical substitution. Part 35. A study of the effect of solvent on atomic chlorination of 1,1-dichloroethane

A study has been made of the changes in selectivity observed when atomic chlorination of 1,1-dichloroethane is performed in the gas phase and in the liquid phase in various solvents. In the liquid phase, selectivity is affected by the polarisability of the solvent. Chlorination in fluorocarbons or their derivatives shows a selectivity similar to the gas phase; chlorination in unreactive polarisable solvents is much less selective whereas chlorination in aromatic solvents is as selective as the gas phase and in carbon disulphide is much more selective, probably due to the formation of a π-complex and an adduct radical (CS₂Cl·) respectively.