1,2,4-三嗪类化合物的研究——Ⅶ.N-[5′-(3′-甲硫基-6′-乙氧羰基)-1′,2′,4′-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯的制备及其置换反应  

CHEMISTRY OF 1,2,4-TRIAZINE——Ⅶ.THE PREPARATION AND SUBSTITUTION REACTION OF ETHYL N-[5'-(3'-METHYLMERCAPTO-6'-ETHOXYCARBONYL)-1',2',4'-TRIAZINYL]-3-METHYLMERCAPTO-5-OXO-1,2,4-TRIAZINE-6-CARBOXYLATE

作　　者：蔡孟深 程铁明 朱文君 陈文政 王少农 

机构地区：[1]北京医学院药学系

出　　处：《化学学报》1985年第5期454-459,共6页Acta Chimica Sinica

摘　　要：本文报道了N-[5'-(3'-甲硫基-6'-乙氧羰基)-1',2',4'-三嗪基]-3-甲硫基-5-氧代-1,2,4-三嗪-6-羧酸乙酯(3)的制备及其与胺、酚类化合物的反应.3a 的结构经元素分析、红外光谱、质谱、核磁和紫外光谱的分析结果推定.3a 与一系列胺及酚发生置换反应,分别得到了相应的5-胺基-3-甲硫基-1,2,4-三嗪-6-羧酸乙酯(5、6、7、8)和5-芳氧基-3-甲硫基-1,2,4-三嗪-6-羧酸乙酯(12、13、14、15、16);3a 与对甲苯胺反应,除了生成5-胺基产物外,还能得到3-胺基-5-羟基-1,2,4-三嗪-6-羧酸乙酯(9)和3,5-双胺基-1,2,4-三嗪-6-羧酸乙酯(10);当3a 与水合肼(90%)反应时,则得到N,N'-双[5'-(3'-甲硫基-6-乙氧羰基)-1,2,4-三嗪基]肼(11).The preparation and chemical transformations of ethyl N-[5′-(3′-methylmercapto-6′-ethoxycarbonyl)-1′,2′,4′-triazinyl]-3-methylmercapto-5-oxo-1,2,4-triazine-6-carboxylate(3a)were reported.3a was obtained by treating ethyl 3-methylmercapto-5-oxo-1,2,4-triazine-6-carboxylate(1)in the presence of pyridine withp-toluenesulfonylchloride in benzene and then water.3a reacted with a series of aromatic amines in hot ethanol to give ethyl 5-substitutedamine-3-methylmercapte-1,2,4-triazine-6-carboxylates(5,6,7,8).No reaction tookplace when isobutylamine was used.When compound 3a was reacted with p-toluidinein hot ethanol,ethyl 3-toluidino-5-hydroxy-1,2,4-triazine-6-carboxylate(9)andethyl 3,5-ditoluidino-1,2,4-triazine-6-carboxylate(10)were obtained in addition tothe ethyl 5-substituted amino-3-methylmercapto-1,2,4-triazine-6-carboxylate (8).When compound 3a was reacted with hydrazine(90%),the N,N′-bis[5-(3-methyl-mercapto-6-ethoxycarbonyl)-1,2,4-triazinyl]-hydrazine(11)was obtained.Compound 3a reacted with p-cresol,guaiacol,p-methoxyphenol,p-nitrophenol ando-nitrophenol in ethanolic pyridine at room temprature to give the corresponding ethyl3-methylmercapto-5-aryloxy-1,2,4-triazine-6-carboxylate(12,13,14,15,16).

关 键 词：甲硫基 烷硫基 置换反应 对甲苯胺 反应时 乙氧羰基 烷氧羰基 三嗪 氮杂环化合物 收率 羧酸 乙酯 脂族酯 

分 类 号：O62[理学—有机化学]