Participation of a heterolytic path in the photochemistry of chlorobenzene

The photochemistry of chlorobenzene in different media has been studied in the presence of oxygen as well as of allyltrimethylsilane and benzene. These are selective traps of the phenyl radical and of the phenyl cation, respectively. Photo-homolysis is a primary process, under most conditions the main processes. However, in an acidic alcohol such as 2,2,2-trifluoroethanol (TFE), this is substituted by photoheterolysis, though with a lower efficiency.