Gas-Phase Atomic Halogenation Reactions Using Iodine Monochloride

Article abstract of DOI:10.1021/jo00354a008

The mechanism of the photoinitiated gas-phase halogenation reactions of alkanes using iodine monochloride has been reported previously as proceeding via a radical chain process to form the corresponding alkyl chlorides.This is in marked contrast to analogous reactions with bromine-chlorine mixtures, thought to form bromine chloride, which produce alkyl bromides via a radical process.An attempt has been made to rationalize this anomaly.In this paper evidence is offered to demonstrate that under photolytic conditions, alkanes and iodine monochloride react via a radical chain process to produce initially the corresponding alkyl iodide.The reaction is shown to proceed by a chain process where the chain-carrying species is the chlorine atom.However, the reaction is complicated by further ionic reactions of the alkyl iodides, whith iodine monochloride, which produce alkyl chlorides and other polyhalogenated materials.