Direct Experimental Evidence for Alkoxyl Radicals Reacting as Hydrogen Atom Donors toward Pyridines

Nanosecond transient absorption spectroscopy was used to generate ethoxyl radicals and demonstrate that they react with 2,6-lutidine and 4-phenylpyridine to give the corresponding N-hydropyridinyl radicals-products of a novel hydrogen atom transfer from the alkoxyl radical to the nitrogen atom of the substituted pyridines. Nanosecond kinetics show that both reactions are rapid (k ∼ 10⁷ M^-1 s^-1) in acetonitrile at room temperature. Rate constants measured for reaction of the ethoxyl vs. d₅-ethoxyl radical with 2,6-lutidine and 4-phenylpyridine show that both reactions exhibit primary H/D kinetic isotope effects for the hydrogen (deuterium) atom transfer reactions.