Synthesis and properties of N-methylmorpholinium 4aryl-6-methyl-5-phenylcarbamoyl-3cyano-1,4dihydropyridine-2-thiolates. Molecular and crystalline structure of 2allylthio-6-methyl-5-phenylcarbamoyl-4-(2chlorophenyl)-3-cyano-1,4-dihydropyridine

By the condensation of an aromatic aldehyde, the anilide of acetoacetic acid, cyanothioacetamide, and Nmethylmorpholine, substituted N-methylmorpholinium 1,4-dihydropyridine-2-thiolates have been synthesized and subsequently used in the synthesis of the corresponding thiones, 2-alkylthiopyridines, thieno[2, 3b]pyridines, and disulfides. X-ray diffraction has been used to establish the structure of 2-allylthio-6-methyl-5phenylcarbamoyl-4-(2-chlorophenyl)-3-cyano-1, 4-dihydropyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1243–1251, September, 1996. Original article submitted May 13, 1996.     

Propanal in the Syntheses of Alkyl-substituted 3-Cyano-2-piperidone, 3-Cyano-2,5,6,7-tetrahydropyrindin-2(1H)-one, and 3-Cyanopyridine-2(1H)-thione

Condensation of propanal with cyanothioacetamide and morpholine gave 3-cyano-4-ethyl-5-methyl-6-morpholino-2-piperidone, the structure of which was studied by X-ray analysis. Reaction of propanal with cyanothioacetamides and cycloalkanone enamines gave 3-cyano-4-ethyl-2,5,6,7-tetrahydropyrindin-2(1H)-one and 3-cyano-4-ethyl-5,6-hexamethylenepyridine-2(1H)-thione. The latter was used for the preparation of substituted 2-benzyloxycarbonylmethylthiopyridine and 3-amino-2-benzyloxycarbonylthieno[2,3-b]pyridine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1053–1059, July, 2005.     

Synthesis of esters ofpara-hydroxy substituted α-trifluoromethylmandelic acids

Methyl trifluoropiruvate in trifluoroacetic acid at 20 °C rapidly C-hydroxyalkylates various phenols at thepara-positions to afford the corresponding esters ofpara-hydroxy substituted -trifluoromethylmandelic acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 528–530, March, 1995.The present study was carried out with the financial support of the Russian Foundation for Basic Research (Project code 93-03-22696).     

A new method for the synthesis ofN-methylmorpholinium 4-aryl-5-cyano-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates and their properties

N-Methylmorpholinium 4-aryl-5-cyano-2-oxo-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates were obtained by the condensation of aromatic aldehydes, cyanothioacetamide, and Meldrum's acid in the presence ofN-methylmorpholine. They were then used in the syntheses of substituted 6-alkylthio-3,4-dihydropyridin-2(1H)-ones and 4,5-dihydrothieno[2,3-b]pyridin-6(7H)-ones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1852–1856, October, 1997.     

Synthesis of Ammonium 5-Arylcarbamoyl-4-heteryl-6-methyl-3-cyano-1,4-dihydropyridine-2-thiolates and 4-Heteryl-5-carbamoyl-6-methyl-3-cyano-1,4-dihydropyridine-2-selenolates

The condensation of enamines derived from acetoacetanilides, heterocyclic aldehydes, and cyanothioacetamide yielded ammonium 5-arylcarbamoyl-5-heteryl-6-methyl-3-cyano-1,4-dihydropyridine-2-thiolates, which were subsequently used for the synthesis of substituted 2-alkylthio-1,4-dihydropyridines, 2-alkylthiopyridines, and thieno[2,3-b]pyridines. The reaction of acetoacetamide with heteroaromatic aldehydes and cyanoselenoacetamide in the presence of N-ethylmorpholine yielded N-ethylmorpholinium 4-heteryl-5-carbamoyl-6-methyl-3-cyano-1,4-dihydrolyridine-2-selenolates, from which substituted 2-alkylseleno-1,4-dihydropyridines were prepared.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 483–492.Original Russian Text Copyright © 2005 by Dyachenko.     

Synthesis and alkylation ofN-methylmorpholinium 6-amino-3,5-dicyano-4-methylpyridine-2-thiolate

The condensation of acetaldehyde with a twofold excess of cyanothioacetamide andN-methylmorpholine givesN-methylmorpholinium 6-amino-3,5-dicyano-4-methylpyridine-2-thiolate. This compound is also formed by recyclization of 2,6-diamino-3,5-dicyano-4-methyl-4H-thiopyran. From this pyridinethiolate, several substituted 2-alkylthiopyridines and 3,6-diamino-5-cyano-4-methyl-2-methoxycarbonylthieno[2,3-b]pyridine were obtained.     

Catalytic oxidation of cycloalkane heteroanalogs as a way to polyfunctional compounds

Liquid phase oxidation of cycloalkane diheteroanalogs catalyzed by compounds of Cu²⁺, Ni²⁺, Co²⁺, Cr³⁺, Fe³⁺ has been studied. It has been established that these catalysts can be applied to intensify, oxidize and increase the selectivity of this process.

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: Cu², Ni²⁺, Co²⁺, Cr³⁺, Fe³⁺. .

     

Synthesis and the reactions of trifluoromethylated 1,2,3-triketones 2-(het)arylhydrazones and 4,7-dihydroazolo[5,1-c]triazines

The coupling of trifluoromethylated 1,3-diketones with (het)aryldiazonium chlorides results mainly in the formation of 1,2,3-triketones 2-(het)arylhydrazones while using hetarylamine with a NH-group at the α-position of the heterocycle as the diazonium component gives 4,7-dihydroazolo[5,1-c]triazines due to cyclization at the trifluoroacetyl fragment. Trifluoromethylated 1,2,3-triketones 2-(het)arylhydrazones and 7-hydroxy-4,7-dihydroazolo[5,1-c]triazines react regio-selectively with methyl hydrazine and phenyl hydrazine to form 3-CF₃-pyrazoles. The long-range coupling constants (J_F-H) of 1-methylpyrazoles and the chemical shifts of trifluoromethyl groups in the ¹⁹F NMR spectra can be used for the determination of regio-isomeric structures of mono(trifluoromethyl)-substituted pyrazoles. 2-(Het)arylhydrazones and 4,7-dihydroazolo[5,1-c]triazines with two trifluoromethyl substituents afford the mixtures of cis- and trans-azopyrazoles in the reactions with hydrazines.     

New 4,4-bis(trifluoromethyl)-4H-1,3,2-benzodioxaphosphinine 2-oxides(sulfides)

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Synthesis and properties of N-methylmorpholinium 6-methyl-4-(4-pyridyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate

Condensation of acetoacetic acid anilide, 4-pyridyl aldehyde, cyanothioacetamide and N-methylmorpholine gave N-methylmorpholinium 6-methyl-4-(4-pyridyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate from which were obtained the corresponding substituted pyridinethiones, 2-alkylthio-1,4-dihydropyridines and 3-amino-2-benzoyl-6-methyl-4-(4-pyridyl)-5-phenylcarbamoylthieno[2,3-b]pyridine.T. G. Shevchenko Lugansk Pedagogical Institute, Lugansk 348011. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 672–675, May, 1997.