Mechanisms of the reactions of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides

Abstract

The rearrangements of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides have been carried out to clarify the mode of migration of the arenesulfonoxy group by means of both 18O tracer and kinetic experiments. In the rearrangements of N-arenesulfonoxy-iso-carbostyril and carbostyril, the main migration route of the arenesulfonoxy group is via the solvent separated ion pair path with a minor portionpassing throug step appears to be NO bond cleavage. For 1-amino-iso-quinoline N-oxide the migration of tosyloxy group to 1-amino-4-tosyloxyiso-quinoline through the oxygen-bridged ion pair pathway is so fast that the presence of the anhydro base cannot be detected. Reaction of 2-aminoquinoline N-oxide to afford 2-amino-6-tosyloxyquinoline which involves migration to a distant position proceeds rapidly, apparently through the solvent separated ion pair path.