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Reaction of Ethoxymethylenemalonate with Cyanothioacetamide in the Presence of Triethylamine: Formation of 1,5-Diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and Unexpected Aminomethylation Result

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Abstract

The reaction of cyanothioacetamide with ethoxymethylenemalonate and triethylamine in ethanol upon heating is non-selective and leads to the formation of a mixture of triethylammonium 1,5-diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate with a predominance of the latter. When treating with primary amines and 37% formalin in boiling aqueous alcohol, the reaction product gives only 4-(1,3,5-thiadiazinan-2-ylidene)-2-(3,4-dihydro-2H-1,3,5-thiadiazin-6-yl)pent-2-enedinitrile instead of the expected pyrido[2,1-b][1,3,5]thiadiazine derivatives. Triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate does not react under these conditions.

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Funding

This work was financially supported by the Ministry of Education and Science of the Russian Federation (project no. 0795-2020-0010, V.V. Dotsenko).

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Authors and Affiliations

  1. Kuban State University, 350040, Krasnodar, Russia

    V. V. Dotsenko & S. G. Krivokolysko

  2. North Caucasus Federal University, 355009, Stavropol, Russia

    V. V. Dotsenko

  3. Institute of Chemical Reagents and High Purity Chemical Substances of National Research Center “Kurchatov Institute”, 107076, Moscow, Russia

    E. A. Chigorina

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  1. V. V. Dotsenko
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Dotsenko, V.V., Krivokolysko, S.G. & Chigorina, E.A. Reaction of Ethoxymethylenemalonate with Cyanothioacetamide in the Presence of Triethylamine: Formation of 1,5-Diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and Unexpected Aminomethylation Result. Russ J Gen Chem 90, 590–596 (2020). https://doi.org/10.1134/S1070363220040052

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