ピリジン誘導体の合成研究 (第11報)

ピコリンN-オキシド類の無水酢酸による転位反応機構について

抄録

In connection with rearrangement reaction in picoline 1-oxides, the first step of rearrangement is the addition of CH₃CO⁺ to N-O and this is largely influenced by basicity of N-oxides, the reaction being difficult under mild conditions in compounds with negative pKa values. Rate-determining step in this reaction was assumed to be the severance of N-O bond in N-OCOCH₃. Reaction rate of quinaldine 1-oxide to 2-quinolinemethanol acetate was examined and it was revealed that the reaction was of the first order and progressed in a sharp, straight line. It was thereby concluded that this rearrangement is an ionic reaction and that the rearrangement of picolines to alcohol acetates also progressed by similar ionic reaction.