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

利用<α>-氨基腈的特性开发有机合成化学

基本信息

批准号：
60550602
负责人：
TAKAHASHI Kazumasa
金额：
$ 1.41万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

项目摘要

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.

1.α<alpha>-酮酰胺作为合成氨基酸和青霉素类似物的重要中间体已被广泛应用。本文报道了一种合成α-酮酰胺的有效方法<alpha>，它是由α<alpha>-（N-甲基苯胺基）乙腈（1）与酯类反应生成<beta>α-羟基-α<alpha>-氰基烯胺（2），再<alpha>经醋酸铜（II）水解得到相应的α-酮酰胺（3）。2与水合肼或一甲基肼反应，得到氨基吡唑（4）.丁二醛与伯烷基胺和伯芳基胺的Strecker反应以高产率得到了1-取代的2，5-二氰基吡咯烷（6），并讨论了它们的立体化学。顺式和反式异构体之间的差异在熔点、Rf值和<^1H> -NMR光谱的物理性质中得到了明显的统一。以6为原料合成了有用的二酮类和吡咯烷类生物碱。