New method for obtaining 3-cyano-1,4-dihydropyridine-2(3H)-thiones

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, p. 1142, August, 1988.     

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.     

Synthesis, Structure, and Some Properties of Substituted 3-Carbethoxy(methoxy)-5-cyano-1,2,3,4-tetrahydrospirocyclohexane-4-pyridine-2-thiones

The condensation of cyclohexylidenemalononitrile or cyclohexylidenecyanoacetic ester with thioamidoethyl(methyl)malonate in the presence of sodium ethylate gave 6-amino-3-carbethoxy-5-cyano-4-spirocyclohexane-1,2,3,4-tetrahydropyridine-2-thione and 3-carbethoxy(methoxy)-5-cyano-6-oxo-4-spirocyclohexanepiperidine-2-thiones which were used in the synthesis of the corresponding substituted 2-alkylthiotetrahydropyridines. 5-Carbethoxy-3-cyano-3-methyl-6-methylthio-4-spiro-cyclohexane-3,4-dihydropyridine-2(1H)-one was studied by X-ray crystallography.     

Regioselective synthesis and properties of 3-cyano-6-thienylpyridine-2(1H)-thiones

Reactions of sodium derivatives of 2- and 3-thenoylacetaldehydes with cyanothioacetamide gave 2- and 3-cyano-6-thienylpyridine-2(1H)-thiones, which were used in the synthesis of substituted 2-alkylthiopyridines, thieno[2,3-b]pyridines, and other fused heterocycles. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 365–368, February, 1998.     

Synthesis and some properties of 4-alkyl-5-cyano-6-mercapto-3,4-dihydropyridin-2(1H)-ones

Condensation of propionic (or acetic) aldehyde, cyanothioacetamide, Meldrum's acid, andN-methylmorpholine occursvia the intermediate formation of the corresponding Michael adducts and yields 4-alkyl-5-cyano-6-mercapto-3,4-dihydropyridin-2(1H)-ones. The oxidation of the reaction products with DMSO and their alkylation were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2016–2019, November, 1997.     

Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization

The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroal-kynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0℃. Intramolecular elimination of Ph3PO took place when compound 5 was heated in aqueous methanol at 115-120℃ in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, 1H NMR, 19F NMR and 13C NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.     

Synthesis of 3-cyano-4-aryl-5-ethoxycarbonyl-6-methyl-3,4-dihydropyridine-2-thiones

The condensation of ethyl arylidenacetoacetate with cyanothioacetamide and of arylidenecyanothioacetamides with ethyl acetoacetate or of arylidenecyanothioacetamides with ethyl -aminocrotonate gave 3-cyano-4-aryl-5-ethoxycarbonyl-6-methyl-3,4-dihydropyridine-2-thiones. PMR spectroscopy showed that the 3-cyano-4-aryl-3,4-dihydropyridine-2-thiones are formed as a mixture of cis and trans isomers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 95–102, January, 1985.     

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 properties ofN-methylmorpholinium 6-amino-3,5-dicyano-1,4-dihydropyridine-4-spirocyclopentane-2-thiolate

The reaction of cyclopentylidenecyanothiocetamide with cyanothioacetamide andN-methylmorpholine gaveN-methylmorpholinium 6-amino-3,5-dicyano-1,4-dihydropyridine-4-spirocyclopentane-2-thiolate, which was used in the syntheses of substituted 2-alkylthiodihydropyridines and pyrazolodihydropyridine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1849–1851, October. 1997.     

3-Cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines in the synthesis of substituted 3-(aminomethyl)pyridines

The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.     

Synthesis and properties of 5-acetyl-3-cyano-4-isobutyl-6-methyl-3,4-dihydropyridine-2(1H)-thione

Condensation of isovaleric aldehyde with cyanothioacetamide and acetylacetone or its enamine produces 5-acetyl-3-cyano-4-isobutyl-6-methyl-3,4-dihydropyridine-2(1H)-thione, from which 5-acetyl-3-cyano-4-isobutyl-6-methylpyridine-2(1H)-thione and the corresponding substituted 2-alkylthio-1,4-dihydropyridines are prepared. T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011, Ukraine; e-mail: kgb@lgpi.lugansk.ua; N. D. Zelinskii Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow 117913, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 516–519, April, 1999.     

Preparation and properties of betaines of 4-pyridyl-3,4-dihydropyridine-2-thiones(1H)

Condensation of 2-cyano-3-pyridylthioacrylamides with esters of acetoacetic or -aminocrotonic acids yields betaines of 3,5,6-substituted-4-pyridyl-3,4-dihydropyridine-2-thiones(1H). The spectral characteristics of the betaines have been examined and their ionization constants (pK) determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 630–635, May, 1986.     

Synthesis of annulated heterocyclic systems based on 4-CF3- or 4-CHF2-3-cyano-(1H)-pyridine-2-thiones

A simple and convenient preparative method for the synthesis of 3-cyano-4-difluoro- and -trifluoromethylpyridine-2(1H)-thiones was developed. During studies of synthetic potential of these compounds, approaches to the synthesis of a number of annulated heterocyclic systems were suggested.     

Synthesis of 4-alkyl-3-cyano-5,6,7,8-tetrahydroquinoline-2(1H)-thiones and their derivatives

4-Alkyl-3-cyano-5,6,7,8-tetrahydroquinoline-2(1H)-thiones, used in synthesis of substituted 2-alkylthioquinolines and thieno[2,3-b]pyridines, were obtained by condensation of cyanothioacetamide, aliphatic aldehydes, and morpholinocyclohexene.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011 Ukraine. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913 Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 81–85, January, 1998.     

Synthesis of 6-substituted 3-cyano-5-nitropyridine-2(1H)-thiones

The reactions of 1-substituted 2-nitro-3-phenylaminoprop-2-en-1-ones with cyanothioacetamide afforded the corresponding 6-substituted 3-cyano-5-nitropyridine-2(1H)-thiones, which were used for the synthesis of 6-substituted 3-cyano-2-methylthio-5-nitropyridines and 7-substituted 4-hydroxy-8-nitropyrido[2",3":4,5]thieno[2,3-b]pyridin-2(1H)-ones.     

Synthesis and hydrolytic cleavage of 1-aryl-5-cyano-6-(2-dimethylaminovinyl)-4-oxo(thioxo)-1,4-dihydropyrimidines

1-Aryl-5-cyano-6-(2-dimethylaminovinyl)-4-oxo-1,4-dihydropyrimidines and their 4-thioxo analogs, which were prepared in three steps from cyanoacetamide and cyanothioacetamide, respectively, were subjected to hydrolysis. In aqueous AcOH, hydrolysis of N-(dimethylaminomethylene)-2-cyano-5-dimethylamino-2,4-pentadieneamide derivatives containing amino groups at position 3 afforded formylpyridones. The reaction of 2-cyano-3-dimethylaminothiocrotonamide with DMF dimethyl acetal gave rise to 3-cyano-4-dimethylamino-2-methylthiopyridine.     

Synthesis and alkylation ofN-methylmorpholinium 5-cyano-4-(3- and 4-hydroxyphenyl)-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates

The reactions of 3- or 4-hydroxybenzaldehydes with cyanothioacetamide and Meldrum's acid in the presence ofN-methylmorpholine affordedN-methylmorpholinium 5-cyano-4-(3-or 4-hydroxyphenyl)-2-oxo-1,2,3,4-tetrahydropyridine-6-thiolates, respectively. The resulting compounds were used in the synthesis of substituted 6-alkylthio-1,2,3,4-tetrahydropyridin-2-ones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2333–2336. December, 1999.     

Synthesis of N-Substituted Derivatives of 3-(1,4-Benzodioxan-2-yl)-4-phenyl-1,2,4-triazole-5(4H)-thiones

Russian Journal of Organic Chemistry - The addition of 5-(1,4-benzodioxan-2-yl)-4-phenyl-4H-1,2,4-triazole-3-thiol to the C=C double bond of acrylonitrile, acrylamide, and ethyl acrylate afforded...