Photochemical Transformations. 26. Sensitized and Unsensitized Photoreactions of Some Benzyl Chlorides in tert-Butyl Alcohol

Article abstract of DOI:10.1021/jo01294a007

Benzyl chloride and a variety of meta- and para-substituted derivatives have been irradiated in tert-butylalcohol at 254 nm or in acetone-tert-butyl alcohol mixtures at 300 nm.Quantum and chemical yields of photosolvolysis products (benzyl tert-butyl ether and/or benzyl alcohol), photohomolysis products (bibenzyl and 4-phenyl-2-methyl-2-butanol), and corresponding products from substituted benzylchlorides have been measured as functions of substrate concentration and medium composition.Sensitized reactions favor bond heterolysis, but direct irradiations favor homolysis, although reactions are not clean in either case.There is no correlation between quantum yields for photosolvolysis and Hammett ? or Brown ?⁺ constants, and no salt effects of added lithium perchlorate were observed, in either direct or sensitized reactions.