Cinnoline誘導体に関する研究(第2報) : 4-(Methylsulfonyl)-cinnolineに対する求核試薬の反応について

概要

論文の詳細を見る
4-(Methylsufonyl)cinnoline (I) gradually undergoes decomposition when left in air and changes into 4-cinnolinol (IV). I easily undergoes decomposition into IV when heated with water and the decomposition is further facilitated when heated with a dilute acid. When I is heated in aqueous solution of sodium hydroxide or in methanolic solution of sodium methoxide, IV or 4-methoxycinnoline (V) is formed. Application of aniline, hydrazine, or hydroxylamine to I respectively gives 4-anilino-(VI), 4-hydrazino-(VII), or 4-hydroxyamino-cinnoline (VIII) (Chart 2). The methylsulfonyl group in I is substituted also with active methylene (methine) carbanion. For example, reaction of I, in the presence of sodium amide, with ethyl acetoacetate (IXa), ethyl malonate (IXb), ethyl cyanoacetate(IXc), malononitrile(IXd), phenylacetonitrile(IXe), or ethynylbenzene (IXf) respectively affords ethyl 4-cinnolineacetate (Xa'), ethyl 4-cinnolinemalonate (Xb), ethyl α-cyano-4-cinnolineacetate (Xc), 4-cinnolinemalononitrile (Xd), α-phenyl-4-cinnolineacetonitrile (Xe), or 4-(phenylethynyl)cinnoline (Xf) (Chart 3 and Table I).
公益社団法人日本薬学会の論文
1968-01-25