Relative Reactivities of Hetaryl Radicals in Hydrogen Atom Abstraction and Nucleophilic Addition Ractions

Article abstract of DOI:10.1021/jo00171a012

The 3-pyridyl, 4-isoquinolyl and 3-quinolyl ? radicals were generated photochemically from their corresponding halides in the presence of sodium methoxide and thiophenoxide in methanol.Each radical in competition abstracts a hydrogen atom from either methoxide ion or methanol or adds thiophenoxide ion.The corresponding reduction to substitution product ratios give rate constant ratios which are similar for the three hetaryl radicals, showing only a small influence of radical structure on relative reactivity.The thiolate ion is 2-5 times more reactive than methoxide ion; methoxide on the average is 39 times more reactive than methanol.