Cinnoline誘導体に関する研究(第6報) : 4-Cinnolinecarbonitrileと求核試薬との反応について

抄録

Application of nucleophilic reagents to 4-cinnolinecarbonitrile (I) resulted in the two following types of reaction. (1) Attack of the reagent on the carbon atom in the CN group resulting in the addition to the carbon-nitrogen triple bond. (2) Attack of the reagent on the ring-carbon at 4-position, carrying the CN group, resulting in the liberation of this CN group as a cyano ion and in replacement reaction. Heating of I with alkali or acid results in the formation of 4-cinnolinecarboxylic acid (II) by the above (1) type reaction. Application of hydrogen peroxide in alkaline reaction to I produces 4-cinnolinecarboxamide (III), while reaction of I with hydroxyamine gives 4-cinnolinecarboxamidoxime (IV), both being the result of (1) type reaction (Chart 1). On the other hand, reaction of I with sodium methoxide, aniline, and hydrazine respectively produces 4-methoxy-(V), 4-anilino-(VI), and 4-hydrazino-cinnoline (VII), by the (2) type reaction (Chart 2).