N. Mathivanan et al., PHOTOCHEMICAL GENERATION OF RADICAL-ANIONS OF PHOTOLABILE ARYL KETONES, Journal of physical chemistry, 99(20), 1995, pp. 8190-8195
The radical anions of a series of substituted alpha-(aryloxy)acetophen
ones have been generated by trapping the solvated electron produced by
355-nm laser-induced photoionization of 4,4'-dimethoxystilbene in eit
her acetonitrile or dimethylformamide (DMF). The radical anion of the
parent ketone, alpha-phenoxyacetophenone, has lambda(max) at 500 nm an
d decays with a rate constant 7 x 10(5) s(-1). This rate constant refl
ects the rate of beta-cleavage to generate phenoxide ion and phenacyl
radical. The rate constant for beta-cleavage decreases for ketones wit
h electron donating substituents in the alpha-aryloxy ring. Substituen
t effects on the aceotphenone ring are in the opposite direction, and
many of the 4-substituted (aryloxy)acetophenones have half-lives in ex
cess of 10 mu s that reflect a combination of second order processes a
nd are not limited by beta-cleavage. The generality of the photoioniza
tion/electron trapping method for the generation of radical anions of
ketones with short-lived excited states that preclude direct excitatio
n is illustrated by its application to other aryl ketones that undergo
alpha-cleavage, beta-phenyl quenching, and intramolecular hydrogen ab
straction reactions.