Ester photolysis and the meta effect

The pre/ivference for solvolysis of meta substituted esters such as m-nitro-phenyl phosphate and m-methoxybenzyl acetate was discovered by Havinga et and studied further by Zimmerman (equation 50). Radicals can be formed in these reactions, and there is some dispute as to whether radical pairs also lead to ion pairs (equation 50).  

The phenomenon of induced decomposition, in which radicals derived from reaction of the solvent with the initiator benzoyl peroxide consume some of the initiator in a chain process, was first elucidated by Bartlett and Nozaki (equation 51), and by Cass.  

The direct reaction of free radical initiators with non-radical substrates resulting in the formation of free radicalshas been termed molecule-induced homolysis. An example is the reaction of a diacyl peroxide with an alkene (equation 52).  

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Photochemical generation of free radicals from ketones 20 Ester photolysis and the meta effect 21 Induced decomposition of radical initiators 21 Molecule-induced homolysis 22... 

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