REACTION OF ALKANALS AND AMINO-ACIDS OR PRIMARY AMINES - SYNTHESIS OF 1,2,3,5-SUBSTITUTED AND 1,3,4,5-SUBSTITUTED QUATERNARY PYRIDINIUM SALTS
REACTION OF ALKANALS AND AMINO-ACIDS OR PRIMARY AMINES - SYNTHESIS OF 1,2,3,5-SUBSTITUTED AND 1,3,4,5-SUBSTITUTED QUATERNARY PYRIDINIUM SALTS
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DOI：
10.1021/jo01323a012
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发表时间：
1979-01-01
影响因子：
3.6
通讯作者：
ADACHI, S
中科院分区：
文献类型：
--
作者：
SUYAMA, K;ADACHI, S
在室温中性条件下，研究了烷烃与氨基酸或伯胺的缩合反应。由甘氨酸-丙醛和L- α的反应产物。分离鉴定了1-（1-羧甲基）-2-乙基-3,5-二甲基吡啶甜菜碱和1-（1-羧基-3-甲基丙基）-4-乙基-3,5-二甲基吡啶甜菜碱。从乙醇胺-烷醛体系的反应产物中，分离出1、2、3、5位上有4个取代基的吡啶盐。这些甜菜碱吡啶的取代模式与氨基酸异氨基葡萄糖和氨基葡萄糖相似。一个包含。alpha，。beta的机制。提出了-不饱和醛二胺中间体，并有证据表明，n -2-甲基-2-戊二胺乙胺与丙烯在乙酸存在下缩合形成2-乙基-1,3,5-三甲基-和4-乙基-1,3,5-三甲基吡啶盐。在。alpha.，。beta.中添加烷醛。-不饱和醛二胺明显发生区域特异性反应，随后发生环闭合和氧化生成吡啶盐。
The condensation of alkanals and amino acids or primary amines was studied under neutral conditions at room temperature. From the reaction products of the glycine-propanal and L-.alpha.-leucine-propanal system the 1-(1-carboxymethyl)-2-ethyl-3,5-dimethylpyridinium betaine and the 1-(1-carboxy-3-methylpropyl)-4-ethyl-3,5-dimethylpyridinium betaine were isolated and identified. From the reaction products of the ethanolamine-alkanal system, the pyridinium salt with 4 substituents located at the 1,2,3,5 positions was also isolated. The substitution patterns of these pyridinium betaines are similar to those of the amino acids isodesmosine and desmosine. A mechanism involving .alpha.,.beta.-unsaturated aldimine intermediates is proposed, and evidence is presented that 2-ethyl-1,3,5,-trimethyl- and 4-ethyl-1,3,5-trimethylpyridinium salts are formed by condensation of N-2-methyl-2-pentenilidenemethylamine with propanal in the presence of acetic acid. Addition of alkanal to .alpha.,.beta.-unsaturated aldimine apparently occurred regiospecifically and was followed by ring closure and oxidation to give pyridinium salts.