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AMINOMETHYLATION OF MORPHOLINIUM AND N-METHYLMORPHOLINIUM 3,5-DICYANO-4,4-DIMETHYL-6-OXO-1,4,5,6-TETRAHYDROPYRIDINE-2-THIOLATES

Виктор В. Доценко, Константин А. Фролов, Сергей Г. Кривоколыско, Елена А. Чигорина, Татьяна М. Пехтерева, Сергей Ю. Суйков, Елена С. Папаянина, Артем О. Дмитриенко, Иван С. Бушмаринов
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Abstract


The structure of reaction products obtained from 3,5-dicyano-4,4-dimethyl-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolates, primary amines, and formaldehyde substantially depends on the nature of counter-ion (morpholinium or N-methylmorpholinium), as well as on the primary amine structure and the ratio of reactants. Aminomethylation of these thiolates with highly nucleophilic amines RCH2NH2 and excess formalin (2 equiv and more) produced 7-RCH2-9,9-dimethyl-2-oxo-4-thioxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitrile salts, which gave the respective bispidines upon acidification. Performing this reaction with aromatic amines in the case of Nmethylmorpholinium 3,5-dicyano-4,4-dimethyl-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolate led to analogous bispidines, while the morpholinium salt gave 3-aryl-8,8-dimethyl-7-[(morpholin-4-yl)methyl]-6-oxo-3,4,7,8-tetrahydro-2H,6H-pyrido[2,1-b][1,3,5]thiadiazine-7,9dicarbonitriles. The treatment of thiolates with 1 equiv of НСНО and 1 equiv of RCH2NH2 led to 7-RCH2-4-amino-9,9-dimethyl-2-oxo-6thioxo-3,7-diazabicyclo[3.3.1]non-3-ene-1-carbonitriles. The molecular and crystal structures of key compounds were studied in detail by X-ray structural analysis.

How to Cite
Dotsenko, V. V.; Frolov, K. А.; Krivokolysko, S. G.; Chigorina, E. A.; Pekhtereva, T. M.; Suykov, S. Yu.; Papayanina, E. S.; Dmitrienko, A. О.; Bushmarinov, I. S. Chem. Heterocycl. Compd. 2016, 52, 116. [Khim. Geterotsikl. Soedin. 2016, 52, 116.]

For this article in the English edition see DOI 10.1007/s10593-016-1843-5

 


Keywords


bispidines; 3,7-diazabicyclo[3.3.1]nonanes; pyrido[2,1-b][1,3,5]thiadiazines; tetrahydropyridine-2-thiolates; aminomethylation; Mannich reaction; recyclization; tandem reactions; X-ray structural analysis

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