short-lived reaction intermediates
Theoretical, Physical and Computational Chemistry
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The advantage of adding more structure-diagnostic information to the simple detection of flash photolytically generated transient species by changes in UV-visible light absorbance is illustrated by a case study involving the mandelic acid keto-enol system. An early report based on preliminary evidence proposed that flash photolysis of phenyldiazoacetic acid produces the enol of mandelic acid by hydration of phenylhydroxyketene, itself generated by a photo-Wolff reaction of the diazo acid. Further examination, however, shows that this is only a minor route, and that the major pathway is a new enol-forming reaction involving what appears to be hydration of a carboxycarbene formed by dediazotization of the diazo compound. Hydration of phenylhydroxyketene is nevertheless the reaction by which mandelic acid enol is generated when esters of benzoylformic acid are the flash photolysis substrates. These mechanisms, and also identification of the enol as a tranisent species, are supported by detailed arguments involving acid-base catalysis, solvent isotope effects, and the use of oxygen-18 as a tracer. The work produces a keto-enol equilibrium constant for the mandelic acid system, pKE = 16.19, and also acidity constants of the enol ionizing as an oxygen acid, pKEa = 6.39, and the keto isomer ionizing as a carbon acid, pKKa = 22.57. The bearing of these results on the enzyme-catalyzed racemization of mandelic acid is discussed. © 1998 John Wiley & Sons, Ltd.
Type of Medium: