title: Addition-elimination in the reaction of alpha-hydroxyalkyl radicals with 3,5-pyridinedicarboxylic acid and nicotinic acid: example of inner sphere organic electron transfer.
abstract: Reactions of alpha-hydroxyalkyl radicals with 3,5-pyridinedicarboxylic acid (3,5-PDCA) and nicotinic acid (NA) were studied at appropriate pHs in aqueous solutions by pulse radiolysis technique. At pH 1, CH(3)C*HOH and *CH(2)OH radicals were found to react with 3,5-PDCA by rate constants of 2.2 x 10(9) and 5.1 x 10(8) dm(3) mol(-1) s(-1), respectively, giving radical adduct species. The adduct species formed in the reaction of CH(3)C*HOH radicals with 3,5-PDCA underwent unimolecular decay (k = 9.8 x 10(4) s(-1)) giving pyridinyl radicals. Reaction of (CH(3))(2)C*OH, CH(3)C*HOH, and *CH(2)OH radicals with NA at pH 3.3 gave the adduct species which subsequently decayed to the pyridinyl radicals. At pH 1, wherein NA is present in the protonated form, (CH(3))(2)C*OH radicals directly transfer electrons to NA, whereas CH(3)C*HOH and *CH(2)OH radicals react with higher rate constants compared with those at pH 3.3, initially giving the adduct species which subsequently undergo elimination reaction giving pyridinyl radicals. Reactions of alpha-hydroxyalkyl radicals with 3,5-pyridinedicarboxylic acid and nicotinic acid are found to proceed by an addition-elimination pathway that provides one of the few examples of organic inner sphere electron-transfer reactions. Rate constant for the addition reaction as well as rate of elimination varies with the reduction potential of alpha-hydroxyalkyl radicals.
authors.affiliation: Radiation and Photochemsitry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India.
authors.forename: Surajdevprakash B
authors.initials: SB
authors.lastname: Dhiman
authors.forename: Devidas B
authors.initials: DB
authors.lastname: Naik
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D004583:Electrons; D005609:Free Radicals; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D009525:Niacin / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D005609:Free Radicals; D009525:Niacin