Photochemistry of substituted benzyl acetates and benzyl pivalates: A reinvestigation of substituent effects

Article abstract of DOI:10.1021/ja00087a020

The photosolvolysis reactions, in methanol, of six substituted benzyl acetates (7a-f) and benzyl pivalates (8a-f) were studied. Five major benzylic products were formed from two critical intermediates. The ethers (9) were formed from the ion pair, 15, and all of the other products (10-14) were formed from the radical pair, 16. Quenching studies showed that only excited singlet state reactivity was important. The product yields were found to be highly substituent dependent. For instance, for the acetate esters, the yield of ether (9) varied from 2% for X = 4-OCH₃ to 32% for X = 3-OCH₃. Most of the differences in the yields could be attributed to ground state processes that occur after bond cleavage. The important competition is between electron transfer, converting the radical pair to the ion pair, and decarboxylation of RCO₂*. The rates of electron transfer are shown to fit Marcus theory in both the normal and inverted regions. Direct heterolytic cleavage to form the ion pair is of minimal importance.