Photo-Induced -Oxyalkylation of Aryl Chlorides with Ethers and Alcohols through Homolytic Aromatic Substitution

The alpha-oxyalkylation of aryl chlorides with ethers and alcohols using a small amount of a peroxide was found to be induced by photoirradiation. The reaction proceeds through a homolytic aromatic substitution (HAS) mechanism consisting of addition of an alpha-oxyalkyl radical to an aryl chloride and elimination of the chlorine atom to give the alpha-oxyalkylation product, where photoirradiation is considered to effect not only the initiation step to facilitate homolysis of a peroxide, but also the propagating radical chain.