Hydrogen abstraction, ketones biradical behavior

The Norrish Type II reaction of aliphatic and aromatic ketones in isotropic solvents has been studied in considerable detail (26,43), and several aspects of the reaction depend on the conformational mobility of the excited ketone or the 1,4-biradical intermediates formed by y-hydrogen abstraction. In the case of aromatic ketones for example, the triplet lifetime can provide an indication of the facility with which the proper geometry for hydrogen abstraction can be obtained (29,43), the distribution of fragmentation O-cleavage) and cyclization products obtained depends on the conformations available to the triplet 1,4-biradical intermediate and their relative kinetic behavior prior to intersystem crossing (27-30,43-47), and the total quantum yield for the reaction is a function of both of the above factors. For practical reasons, product ratios are usually the easiest aspect of the reaction to monitor, and this is the approach that has been used most commonly in studies of Norrish II reactivity in ordered media (27-30,45). The pertinent features of the triplet state reaction arc illustrated in Scheme 1 (30). 

Photolysis of a carbonyl compound having y-hydrogen commonly gives a shorter chain carbonyl compound, an alkene, and a cyclobutanol, which are formed from a 1,4-biradicaP produced via y-hydrogen abstraction by the excited carbonyl. The photoreactions derived from the 1,4-biradical are termed the Norrish type 11 reaction, and those involving intramolecular hydrogen abstraction from y- and other positions are generically referred to as the type II family. The chemical behavior of the 1,4-biradical determines the type 11 reactivity of carbonyl compounds. In this chapter, the influence of environment on the formation and behavior of the 1,4-biradical from simple alkyl aryl ketones will be described. Environmental effects on the type 11 reaction have been reviewed. ... 

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