The photosolvolysis reactions, in methanol, of six substituted benzyl acetates (7a-9 and benzyl pivalates @a-9 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-f4) 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 RCOz'. 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.

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The photochemistry in methanol of 1-naphthylmethyl phenyl carbonate (3) and 1-naphthylmethyl benzyl carbonate (4) has been studied. Products resulting from both the 1-naphthylmethyl cation and the 1-naphthylmethyl radical are obtained for 3, but only from the cation for 4. Similar results were obtained for the corresponding 1-naphthylmethyl derivatives 5 and 6 of N-phenyl and N-benzyl carbamic acids. The product yields for all four compounds can be explained by a mechanism of initial homolytic cleavage of the 1-naphthylmethyl carbon–oxygen bond from the excited singlet state. The radical pair generated then partitions between the two pathways: electron transfer to form the ion pair or decarboxylation. For PhO-CO-O• and PhNH-CO-O•, decarboxylation is rapid and competitive with electron transfer. For PhCH2O-CO-O• and PhCH2NH-CO-O•, decarboxylation is slower, electron transfer dominates, and only products from the ion pair are obtained.

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