Reactions of e aq − , H atom and OH radicals with 4-pyridinemethanol (4-PM) and 4-pyridinecarboxaldehyde (4-PCA) have been studied at various pH values using the pulse radiolysis technique. Reaction of e aq − with 4-PM and 4-PCA leads to the formation of pyridinyl and ketyl radicals of 4-PM and 4-PCA, respectively. Ketyl radicals formed from 4-PCA react with the parent molecule to give a dimeric radical species. At pH 7, the equilibrium constant for the dimer formation was determined to be 13 500 M-1. At pH 13 also dimer radical formation was observed. Reaction of e aq − with 4-PM was found to give highly reducing pyridinyl radicals. Reaction of OH radicals with 4-PM gives a mixture of species,viz., OH adducts and radicals formed by H-atom abstraction from the –CH2OH moiety. Radicals formed by H-atom abstraction reaction from 4-PM were found to be reducing in nature. O•– radicals were found to react with 4-PM exclusively by H-abstraction pathway.
Research on Chemical Intermediates – Springer Journals
Published: Oct 9, 2004
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