Flash photolysis of 10-diazo-9(10H)-phenanthrenone in aqueous solution. Hydration of fluorenylideneketene and the fluorene-9-carboxylic acid keto-enol system

Flash photolysis of 10-diazo-9(10H)-phenanthrenone in aqueous solution was found to give two successively formed transient species and to produce fluorene-9-carboxylic acid as the major reaction product. These transients were identified, through solvent isotope effects and the form of acid-base catalysis, as fluorenylideneketene, formed by photo-Wolff reaction of the diazophenanthrenone, and fluorene-9-carboxylic acid enol, formed by hydration of this ketene. Analysis of the rate profile of the enol ketonization reaction produced the first and second ionization constants for the enol ionizing as an oxygen acid, pQ(a)(E) = 2.01 and pQ'(E)(a) = 9.61, respectively. The rate of enolization of fluorene-9-carboxylic acid was also determined, by bromine scavenging, and that, coupled with a literature value of the acidity constant of this acid, allowed evaluation of the two keto-enol equilibrium constants (pK(E) = 9.67 for interconverting un-ionized carboxylic acid and enol and pK'(E) = 8.24 for interconverting singly ionized acid and enol), and it also allowed evaluation of the two carbon acid acidity constants (pQ(a)(K) = 11.67 for ionization of the un-ionized carboxylic acid as a carbon acid and pQ'(K)(a) = 17.85 for ionization of its carboxylate ion as a carbon acid). (All acidity constants are concentration quotients applicable at ionic strength 0.10 M.) These keto-enol equilibrium constants and acid dissociation constants are large because of the enol and enolate ion stabilizing effects of the cyclopentadienyl ring of the fluorenyl group; this ring also makes fluorenylideneketene an unusually reactive substance.