OH radical reaction of 5-substituted uracils: Pulse radiolysis and productstudies of a common redox-ambivalent radical produced by elimination of the 5-substituents

Using a redox titration method in the pulse radiolysis of N2O-saturated pho sphate buffer solution, the redox properties of the intermediate radicals d erived from OH radical reactions of 5-substituted uracils 1c-h (R = F, Cl, Br, NO2, NH2, OH) have been characterized. While the primary intermediates were oxidizing C(5) radicals 2c-h and reducing C(6) radicals 3c-h of the re spective OH adducts, a common allyl-type radical of "redox ambivalence" wit h limiting mesomeric forms of reducing carbon-centered 5-oxo-5,6-dihydroura cil-6-yl radical (4) and oxidizing oxygen-centered uracil-5-oxyl radical (5 ) was secondarily formed via elimination of 5-substituents from 3c-h. The r ate of 5-substituent elimination decreased with varying structures of the 5 -substituents in the order halo > amino, nitro > hydroxy groups. The common radical 4/5 showed weaker reducing/oxidizing abilities than the typical py rimidine C(6) and C(5) radicals. The product study demonstrated that the on e-electron reduction of 5-oxyl radical 5 by N,N,N',N'-tetramethyl-p-phenyle nediamine ((2.0 +/- 0.1) x 10(8) dm(3) mol(-1) s(-1)) increased the yield o f isobarbituric acid (Ih), while the one-electron oxidation of 5-oxo C(6) r adical 4 by tetranitromethane increased the yield of isodialuric acid (6).