Abstract
By using dioxane, a homolytic a-oxyalkylation on heteroaromatic rings was achieved in the presence of ammonium peroxydisulfate. Heteroaromatic bases employed here were the derivatives of quinaldine or lepidine―hydroperchlorates of free bases, N-oxide and its hydroperchlorate (of lepidine), and N-ethoxyquarternary perchlorates. The results are summarized as follows : 1) in every case homolytic oxyalkylation took place to introdube the α-dioxanyl group to the unoccupied 2-or 4-posltion of a quinoline ring ; 2) both the hydroperchlorates of free bases and N-ethoxyquarternary salts gave dioxanyl compounds in excellent yields, however, the latter showed higher reactivities; 3) N-oxide (lepidine 1-oxide) could also be reactive towards the α-oxyalkyl radical to give the dioxane compound of the N-oxide even in a lower yield, These data suggested that the reaction proceeded through a course possibly involving a N-alkoxy -or N-oxo-1, 2-dihydroquinoline intermediate. In hydroxymethylation, it seems that the hydroperchlorates of the free bases had some-what higher reactivity than the N-ethoxy quarternary perchlorates, although both were. hydroxyrnethylated quantitatively.
