Synthesis of 3-cyano-5-ethoxycarbonyl-4-isobutyl-6-methyl-3,4-dihydropyridine-2(1H)-thione by three-component condensation

Condensation of isovaleraldehyde with cyanothioacetamide and ethyl acetoacetate (or its enamine) gives 3-cyano-5-ethoxycarbonyl-4-isobutyl-6-methyl-3,4-dihydropyridine-2(1H)-thione. This compound was used in the synthesis of substituted 1,4-dihydropyridin-2-yl sulfides. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 166–168, January, 1999.     

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 of 3-cyano-3-ethoxycarbonyl-4-methyl-6-phenylpyridine-2(1H)-thione and its alkylation

The condensation of acetaldehyde with cyanothioacetamide and ethyl benzoylacetate in the presence of N-methylmorpholine leads to the formation of 3-cyano-5-ethoxycarbonyl-4-methyl-6-phenylpyridine-2(1H)-thione. Alkylation of the last afforded the corresponding substituted 2-alkythiopyridines.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011, Ukraine. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAN),Moscow 117913, Russia.Translated from Khimiya Geterotsklicheskh Soedinenii, No. 12, pp. 1645–1646, December, 1999.     

Three-component condensation in the synthesis of 4-(2-chlorophenyl)-3-cyano-5-ethoxycarbonyl-6-propyl-3,4-dihydropyridine-2(1H)-thione

Condensation of 2-chlorobenzaldehyde with cyanothioacetamide and ethyl butyroylacetate results in 4-(2-chlorophenyl)-3-cyano-5-ethoxycarbonyl-6-propyl-3,4-dihydropyridine-2(1H)-thione, whose further transformation affords the corresponding substituted 2-methylthio-1,4-dihydropyridine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 173–175, January, 2000.     

Regioselective synthesis and properties of 3-cyano-6-methyl-4-trifluoromethylpyridine-2(1H)-thione. Molecular and crystal structure of 3-cyano-2-ethylthio-6-methyl-4-trifluoromethylpyridine

The reaction of trifluoroacetylacetone with cyanothioacetamide proceeded regioselectively to form 3-cyano-6-methyl-4-trifluoromethylpyridine-2(1H)-thione from which the corresponding 2-alkylthiopyridines and 3-aminothieno[2,3-b]pyridines were obtained. The crystal and molecular structure of 3-cyano-2-ethylthio-6-methyl-4-trifluoromethylpyridine was established by X-ray diffraction analysis.     

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 of 6-methyl-5-phenylcarbamoyl-3,4-dihydropyridinespiro-4-cyclohexane-2(1H)-thione and its derivatives

3-Cyano-6-methyl-5-phenylcarbamoyl-3,4-dihydropyridinespiro-4-cyclohexane-2(1H)-thione was obtained by the condensation of acetoacetic acid anilide with cyclohexylidenecyanothioacetamide. Substituted 2-alkylthio-1,4-dihydropyridines and 3-amino-2-(4-chlorobenzoyl)-6-methyl-5-phenylcarbamoyl-4,7-dihydrothieno[2,3-b]pyridinespiro-4-cyclohexane were synthesized from it. T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011, Ukraine N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1533–1535, November, 1997.     

Synthesis of 3-substituted-4-methyl-5-acetyl-4-thiazoline-2-thione

The reaction of various potassium salts [RNHC(=S)SK, R = N(CH₃)₂, morpholino, piperidino, and hexahydro-1-(1H)-azepinyl] with 3-chloro-2,4-pentanedione in ethanol at 25–30° afforded the 1-acetylacetonyl substitutedaminodithiocarbamates 1–4 [RNHC(=S)SCH(COCH₃)₂]. Under refluxing conditions, the same reactants gave the heterocyclic compounds 5–8. Possible mechanism and supporting ir, nmr and mass spectral data are discussed.     

Synthesis and alkylation of 6-methyl-5-phenylcarbamoyl-3-cyano-4-ethylpyridine-2(1H)thione

By condensation of the anilide of acetoacetic acid, propionaldehyde, and cyanothioacetamide, 6-methyl-5-phenylcarbamoyl-3-cyano-4-ethylpyridine-2(IH)thione has been obtained. In an alkaline medium, this compound is alkylated, forming the corresponding substituted 2-pyridyl sulfides. From these pyridines, substituted thienoj2,3-blpyridines have been synthesized through the Thorpe-Ziegler reaction.T. G. Shevchenko Lugansk Pedagogical Institute, Lugansk 348011. N. D. Zelinskii Institute of Organic Chemistry, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1232–1234, September, 1996. Original article submitted May 13, 1996.     

Synthesis and Crystal Structure of 3-Ethoxycarbonyl-4,6-diphenyl-3,4-dihydropyridine-2(1H)-thione

3-Ethoxycarbonyl-4,6-diphenyl-3,4-dihydropyridine-2(1H)-thione was synthesized by the interaction of benzylideneacetophenone with cyanoacetic ester and hydrogen sulfide. Its structure was investigated by X-ray structural analysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1180–1183, August, 2005.     

Synthesis of Derivatives of 3-Cyano-6-methyl-5-phenylcarbamoylpyridine-2(1H)-thione and 3-Cyano-6-methyl-5-phenyl-carbamoylpyridine-2(1H)-selenone

The reaction of ethoxymethylenacetylacetanilide with cyanothioacetamide or cyanoselenoacetamide in the presence of N-methylmorpholine and alkylating agents gave substituted 2-alkylthio- and 2-alkylselenopyridines and thieno[2,3-b]pyridines.     

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 6-Alkylthio-5-carbamoyl-3-cyano-4-phenyl-3,4-dihydropyridin-2(1H)-ones

Condensation of ethyl benzylidenecyanoacetate with thiocarbamoylacetamide in the presence of an equimolar amount of piperidine produces piperidinium 5-carbamoyl-3-cyano-2-oxo-4-phenyl-3,4-dihydropyridine-6(1H)-thiolate, which is then used in synthesis of the corresponding 6-alkylthiosubstituted 3,4-dihydropyridin-2(1H)-ones. Dedicated to Professor Henk van der Plas on his 70th birthday. Latvian Institute of Organic Synthesis, Riga LV-1006 Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 506–509, April, 1999.     

Three-component condensation in the synthesis of 4-(2-chlorophenyl)-3-cyano-5-ethoxycarbonyl-6-propyl-3,4-dihydropyridine-2(1H)-thione

Condensation of 2-chlorobenzaldehyde with cyanothioacetamide and ethyl butyroylacetate results in 4-(2-chlorophenyl)-3-cyano-5-ethoxycarbonyl-6-propyl-3,4-dihydropyridine-2(1H)-thione, whose further transformation affords the corresponding substituted 2-methylthio-1,4-dihydropyridine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 173–175, January, 2000.     

Synthesis and reactions of 3-cyano-6-methoxymethyl-4-methyl-2(1H)-pyridinethione

Nucleophilic substitution of the chlorine atom in 2-chloro-3-cyano-6-methoxymethyl-4-methylpyridine by mercapto group produces the corresponding 2(1H)-pyridinethione, alkylation of which by halogenated compounds in the presence of KOH proceeds regioselectively to form S-alkyl derivatives. Thorpe—Ziegler cyclization of S-alkyl derivatives, which contain an active methylene group, yields new 3-aminothieno[2,3-b]-pyridines.Kuban State Technological University, Krasnodar 350072, Russia, and N. D. Zelinskii Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow 117913; e-mail: stud@issep.rssi.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 337–341, March, 1999.     

Synthesis and properties of 3-cyano-4-(4-cyanophenyl)-1,4-dihydropyridine-2(3H)-thiones

Piperidinium 3-cyano-4-(4-cyanophenyl)-1,4-dihydropyridine-2(3H)-thiolates were obtained by the condensation of 1,3-dicarbonyl compounds, 4-cyanobenzaldehyde, and cyanothioacetamide in the presence of an equimolar amount of piperidine. The acidification of these thiolates gave the corresponding 1,4-dihydropyridine-2(3H)-thiones and pyridine-2(1H)-thione. Alkylation of 1,4-dihydropyridine-2-thiolates or the reaction mixture of the three-carbon condensation using iodacetamide gave 2-carbamoylmethylthio-1,4,5,6-tetrahydro- or 1,4-dihydropyridines, which were characterized by their conversion to 4,7-dihydrothieno[2,3-b]pyridines.Latvian Institute of Organic Synthesis, LV-1006, Riga, LatviaTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 794–798, June, 2000.