Reaction of Methyl N-Oxido-quinolyl and -isoquinolyl Ketone Oximes with Tosyl Chloride

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The reactions of (E)-methyl 1-oxido-2-quinolyl ketone oxime (V_E), (E)- and (Z)-methyl 1-oxido-4-quinolyl ketone oxide (VII_E and VII_Z) and (Z)-methyl 2-oxido-1-isoquinolyl ketone oxime (IX_Z) with tosyl chloride in the presence of NaOH were investigated to compare the reactivity of the N-oxide with that of the oxime group in the same molecule. In the reaction of V_E, 1-hydroxy-2-(1H)-quinolinone (XII) and 2(1H)-quinolinone (XIII) were obtained by the elimination of the acetoxime group. The mechanism of the formation of XII and XIII is discussed in detail. In the reaction of VII_E, Beckmann rearrangement occurred to afford 4-acetylaminoquinoline 1-oxide(XVIII), while the reactions of VII_Z and IX_Z gave only the tosylates of the oximes. These results demonstrate that there is a large difference of reactivity between the E-form and the Z-form, and further that V_E and VII_E show markedly different chemical behavior.