Ketonization of the unusually acidic elongated enol generated by flash photolytic decarboxylation of p-formylphenylacetic acid in aqueous solution

Rates of photolysis of p-formylphenylacetic acid were measured flash photoytically in perchloric acid and sodium hydroxide solutions, and also in acetic acid, biphosphate ion, and tris-(hydroxymethyl)methaneammonium ion buffers, using H2O and D2O as solvents. The results provide rate profiles and solvent isotope effects, which indicate that photolysis occurs through an elongated enol intermediate. This enol is unusually strongly acidic, by some two to three pQa units, when compared with simple non-elongated enols.Key words: flash photolysis, elongated enols, rate profiles, solvent isotope effects.