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

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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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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Keywords:

  • cyanothioacetamide
  • diethyl ethoxymethylenemalonate
  • aminomethylation
  • Mannich reaction
  • 1,3,5-thiadiazines