Abstract

The reaction of (1-ethoxyethylidene)malononitrile with cyanoacetamide or cyanothioacetamide has yielded 6-amino-4-methyl-2-(thio)oxo-1,2-dihydropyridine-3,5-dicarbonitriles. The resulting pyridine derivatives enter into the aminomethylation reaction with an excess of formaldehyde and primary amines with the formation of previously unknown 8-methyl-6-oxo-3-R-1,3,4,6-tetrahydro-2H-pyrido[1,2-a][1,3,5]triazine-7,9-dicarbonitriles. Further treatment of 6-amino-4-methyl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitrile and its oxygen analog with excess of formaldehyde has led to the formation of 3,10-dimethyl-1,8-dithioxo-5,6,12,13-tetrahydro-1H,8H-dipyrido[1,2-a:1′,2′-e][1,3,5,7]tetrazocin-2,4,9,11-tetracarbonitrile and 6,6′-[methylenedi(imino)]bis(4-methyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile), respectively. These compounds have shown a pronounced antidote effect against the herbicide 2,4-D (2,4-dichlorophenoxyacetic acid) in laboratory and field experiments on sunflower seedlings. Furthermore, 6-amino-4-methyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile has exhibited pronounced anticorrosion properties, acting as an adsorption-type corrosion inhibitor. The mechanism of the anticorrosion action has been investigated in detail using X-ray photoelectron spectroscopy.

中文翻译：

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涉及 6-氨基-4-甲基-2-(硫代)氧代-1,2-二氢吡啶-3,5-二甲腈的曼尼希反应

摘要

(1-乙氧基亚乙基)丙二腈与氰基乙酰胺或氰基硫代乙酰胺反应生成6-氨基-4-甲基-2-(硫代)氧代-1,2-二氢吡啶-3,5-二甲腈。所得吡啶衍生物与过量的甲醛和伯胺发生氨甲基化反应，形成以前未知的8-甲基-6-氧代-3- R -1,3,4,6-四氢-2H-吡啶并[ 1,2- a ][1,3,5]三嗪-7,9-二甲腈。用过量甲醛进一步处理 6-氨基-4-甲基-2-硫代-1,2-二氢吡啶-3,5-二甲腈及其氧类似物，导致形成 3,10-二甲基-1,8-二硫代-5,6,12,13-四氢-1 H ,8 H -联吡啶并[1,2- a :1′,2′- e][1,3,5,7]四唑星-2,4,9,11-四甲腈和6,6'-[亚甲基二(亚氨基)]双(4-甲基-2-氧代-1,2-二氢吡啶-3 ，5-二甲腈），分别。在向日葵幼苗的实验室和田间实验中，这些化合物对除草剂 2,4-D（2,4-二氯苯氧基乙酸）表现出明显的解毒作用。此外，6-氨基-4-甲基-2-氧代-1,2-二氢吡啶-3,5-二甲腈表现出显着的防腐性能，可作为吸附型腐蚀抑制剂。使用 X 射线光电子能谱详细研究了防腐作用的机理。