Chlorination of Unsaturated Compounds in Nonpolar Media: Recognition of competition between polar and radical pathways clarifies the olefin-chlorine reaction.

Our work has shown that the apparently simple chlorination of unsaturated materials in nonpolar media is actually rather complex because of the occurrence of competitive reaction pathways, one polar and one radical. Means of recognizing, predicting, and separating the pathways have been developed, and general characteristics of each with respect to relative rates and product distributions have been elucidated. A most intriguing discovery is that of the spontaneous generation of radicals by interaction of certain unsaturates and chlorine; much more work is needed for clarifying the nature of this unexpected reaction.