Development in Organic Synthetic Chemistry Utilizing The Characteristics of <alpha> -Aminonitriles

1. < α > -酮酰胺作为合成氨基酸和青霉素类似物的重要中间体而广为人知。通过< α > -（n -甲基苯胺）乙腈(1)与酯反应生成< α > -羟基- < α > -氰胺(2)，建立了一种合成< α > -酮酰胺(3)的有效方法，该方法可通过乙酸铜（II）水解生成相应的< α > -酮酰胺(3)，收率高。此外，2与水合肼或单甲基肼反应得到了收率较高的氨基吡唑(4)。丁二醛与伯烷基胺和芳胺的streker反应产率高，并对其立体化学性质进行了讨论。顺式异构体和反式异构体的差异在熔点、Rf值和<^1H> - nmr谱的物理性质中得到了明显的统一。还进行了以6为合成试剂合成有用的二酮类和吡咯烷类生物碱的工作。

1. The utility of <alpha> -keto amides has been well-known as important intermediates for synthesis of amino acids and penicillin analogs. An efficient method for the synthesis of <alpha> -keto amides has been established by employing reactions of <alpha> -(N-methylanilino) acetonitrile (1) with esters to form <beta> -hydroxy- <alpha> -cyanoenamines (2), which could be easily converted into the corresponding <alpha> -keto amides (3) by hydrolysis using copper (II) acetate in good yields. Furthermore, the reaction of 2 with hydrazine hydrate or monomethylhydrazine gave aminopyrazoles (4) in good yields.2. The Strecker reaction of succinaldehyde with primary alkyl- and arylamines affords 1-substituted 2,5-dicyanopyrrolidines (6) in good yields, and their stereo-chemistry is also discussed. The apparent unification for differences between cis- and trans-isomers was recognized in the physical properties of melting points, Rf values, and <^1H> -NMR spectra. The work using 6 as synthetic reagents was also carried out to give useful diketones and pyrrolidine alkaloids.