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 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.     

Cyclization reactions of nitriles. 26. Synthesis,structure, and properties of 2-amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione

2-Amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione has been prepared via treatment of N-cyanodimethyldithioimidate or 1,1-di(methylthio)-2-thiocar-bamoyl-2-cyanoethylene with cyanothioacetamide or cyanamide. The structure of the complex formed between 2-amino-4-methylthio-5-cyano-6(1H)-pyrimidinethione and urea has been studied by x-ray structural analysis. Thieno[2,3-d]pyrimidines and thiazolo[3,2-c]pyrimidinium salts have been synthesized based on the 6(1H)-pyrimidinethione.For Communication 25, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1377–1384, October, 1987.     

Synthesis of 2-alkoxy-6-aryl-5-cyano-4(3H)-pyrimidinones

The reaction of methyl 3-aryl-2-cyano-3-methoxypropenoates 1 with cyanamide and sodium methoxide in methanol afforded after acid hydrolysis the methyl 3-[(aminocarbonyl)amino]-3-aryl-2-cyanopropenoates 4 . By performing the reaction in higher boiling alcohols the 2-alkoxy-6-aryl-5-cyano-4(3H)-pyrimidinones 2 were obtained in good yields.     

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-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 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.     

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.     

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 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 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.     

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-methylmorpholinium 6-methyl-4-(2-thienyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate and its reaction with various functionally substituted methyl halides

Condensation of the anilide of acetoacetic acid, thiophene aldehyde, cyanothioacetamide and N-methyl-morpholine gave N-methylmorpholinium 6-methyl-4-(2-thienyl)-5-phenylcarbamoyl-3-cyano-1,4-dihydropyridine-2-thiolate which reacted with various halides ZCH₂Hal or H₂NCOCH(Ph)Cl to give substituted 2-ZCH₂-thio or 2-H₂NCOCH(Ph)-thio-1,4-dihydropyridines.     

Synthesis of ethyl 5-cyano-6-hydroxy-2-methyl-4-(1-naphthyl)-nicotinate

A novel ethyl 5-cyano-6-hydroxy-2-methyl-4-(1-naphthyl)-nicotinate is successfully synthesized and the structure is determined by XRD, GC-MS analysis, element analysis and NMR spectroscopic in detail. A reaction mechanism for the reaction is proposed.     

Synthesis and characterization of 2-(4-aryl-3-cyano-6-methylpyridin-2(1H)-ylidene)malononitriles

The synthesis of pyridine derivatives containing a buta-1,3-diene-1,1,3-tricarbonitrile fragment via the base-promoted reaction of benzalacetones and malononitrile dimer with subsequent oxidation is described. The influence of the substituents on the spectral-luminescent and electrochemical properties was also investigated.     

Synthesis and herbicidal activity of (Z)-ethoxyethyl 2-cyano-3-(2-methylthio-5-pyridylmethylamino)acrylates

2-Methylthio-5-pyridinemethylene amine was prepared from 2-chloro-5-methylpyridine. Ethoxyethyl 2-cyano-3,3-dimethylthioacrylate was prepared from ethoxyethyl cyanoacetate, carbon disulfide, and dimethyl sulfate in 86.2% yield. Its reaction with 2-methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methylthio-3-(2-methylthio-5-pyridylmethylamino)acrylate. Ethoxyethyl (Z+E)-2-cyano-3-ethoxyacrylate was synthesized from ethoxyethyl 2-cyanoacetate and triethyl or- thoacetate in 90.7% yield, and its reaction with 2- methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyri-dylmethylamino)acrylate. The structures of all of the products were confirmed by ¹H NMR, elemental analysis, IR, and mass spectroscopy. The herbicidal activities of the products were evaluated, and the results of bioassay showed that (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyridylmethylamino)acrylate exhibits good herbicidal activity on rape (Brassica napus) at a dose of 1.5 kg/ha. © 2003 Wiley Periodicals, Inc. 15:67–70, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10214     

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 4-methylthio-2(1H)-pyridone derivatives using ketene dithioacetals

Reaction of various active methylene compounds with ketene dithioacetals, bis(methylthio)methylenemalononitrile (1a) and bis(methylthio)methylenecyanoacetamide (1b) gave the corresponding 3-cyano-4-methylthio-2(1H)-pyridone derivatives. The transformation of 4-methylthio-2-oxo-2H-pyran-3-carbonitrile in-to 4-methylthio-2(1H)-pyridone derivatives was also described.     

Synthesis and Crystal Structure of 1-Methylsulfinyl-1-methylthio-2-cyano-2-phenylethylene

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