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我们企图由1-酮-1,2,3,4-四氢菲-2-乙腈(Ⅴ)与氢卤酸作用,合成内酰胺化合物(ⅩⅢ),但得到了意外的结果。γ-酮腈(Ⅴ)与氢卤酸作用,在冰乙酸介质中所得产物为r-酮酰胺(Ⅵ)。在氯仿介质中用溴化氢反应所得产物为(Ⅵ)。用氯化氢反应所得产物为(Ⅶ)。文中对所得产物(Ⅵ),(Ⅶ),(Ⅷ)的结构都进行了证明。γ-酮腈(Ⅴ)是由1-酮-1,2,3,4-四氢菲(Ⅰ)经由Mannich反应,获得1-酮-2[N-(双甲基)氨次甲基]-1,2,3,4-N氢菲盐酸盐(Ⅱ)。(Ⅱ)经咸离后与硫酸二甲酯反应形成季铵盐(Ⅲ)。(Ⅲ)在甲醇-水介质中与氰化钾反应先析出含次甲基化合物(Ⅳ)。后者在甲醇-水介质中与氰化钾继续温热而形成1-酮-1,2,3,4-四氢菲-2-乙腈(Ⅴ)。各步反应得率都不错。
We attempted to synthesize the lactam compound (XIII) by the action of 1-keto-1,2,3,4-tetrahydrophenanthrene-2-acetonitrile (V) with hydrohalic acid, but unexpected results were obtained. The γ-ketonitrile (V) is reacted with hydrohalic acid and the product obtained in glacial acetic acid is r-ketoamide (Ⅵ). The product obtained by the reaction of hydrogen bromide in chloroform medium is (VI). The product obtained by the reaction with hydrogen chloride is (VII). The structure of the resulting products (Ⅵ), (Ⅶ) and (Ⅷ) were all proved. The γ-ketonitrile (V) is obtained by a Mannich reaction of 1-keto-1,2,3,4-tetrahydrophenanthrene (I) to give 1-keto-2 [N- (bismethyl) aminomethanyl] -1,2,3,4-N hydrophyll hydrochloride (II). (Ⅱ) salty and after reaction with dimethyl sulfate to form quaternary ammonium salt (Ⅲ). (III) The methine compound (IV) is first precipitated by the reaction with potassium cyanide in a methanol-water medium. The latter is further warmed with potassium cyanide in a methanol-water medium to form 1-keto-1,2,3,4-tetrahydrophenanthrene-2-acetonitrile (V). The reaction rate of each step is good.