Regioselective conversion of 3-cyano-6-hydroxy-2-pyridones into 3-cyano-6-amino-2-pyridones

The reaction of a tautomeric mixture of 1-butyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxopyridine-3-carbonitrile and its 2-hydroxy-6-oxo analog with phosphorus oxychloride gave 1-butyl-6-chloro-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile (68%) and 1-butyl-2-chloro-1,6-dihydro-4-methyl-6-pyridine-3-car-bonitrile (3%). Both chloropyridones were converted to their corresponding aminopyridones by reaction with liquid ammonia. Strong support for the molecular structure of 6-amino-1-butyl-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile was obtained on the basis of nmr techniques.     

Synthesis of substituted 2-amino-3-cyano-4-methylpyrroles

A facile route for the synthesis of substituted 2-amino-3-cyano-4-methylpyrroles from N-acetyl-α-amino ketones and malononitrile is reported.     

Synthesis of N-substituted 3-hydroxy-2-methyl-4-pyridones and -pyridonimines

Carbohydrates with 1,4 glycosidic bonds like maltose, lactose, dextrin or starch react with primary amines as well as amino acids or proteins to give i.e. 3-hydroxy-2-methyl-4-pyridones 5 and 3-hydroxy-2-methyl-4-pyridonimines 7. A generally applicable synthesis of compounds of this type is described. The pyridones 5 and pyridonimines 7 are strongly complexing agents. Molybdenum-derivatives, for instance, are suitable as fairly stable oxidation catalysts.     

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-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.     

Chelate synthesis of 1-alkyl-2-methyl-3-cyano-4-pyridones from diacetylketene N,S-acetal

N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1455–1456, June, 1992.     

Synthesis and structure of 2-amino- 5-azolyl-3-cyano-4H-pyrans

Previously unknown 5-azolylpyrans were obtained by reactions ofN-acetonyl- andN-phenacylimidazoles, -triazoles, and -tetrazoles with arylmethylenemalononitriles. The structure of 2-amino-3-cyano-6-methyl-5-(5-nitrotetrazol-2-yl)-4-phenyl-4H-pyran was established by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2050–2055, August, 1996.     

Preparative synthesis of 3-cyano-4-difluoromethyl- and 3-cyano-4-trifluoromethyl-2(1H)-pyridones

An efficient procedure for the synthesis of 3-cyano-4-difluoromethyl- and 3-cyano-4-trifluoromethyl-2(1H)-pyridones was developed. The structure of one of the resulting compounds was established by X-ray diffraction analysis.     

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.     

Cyclocondensation of 3-aryl-2-cyano-2-butenoic acid esters with schiff bases

The condensation of ethyl 3-aryl-2-cyano-2-butenoates with benzylideneanilines in the presence of aluminum chloride affords 1,4,6-triaryl-2-oxo-1,2,5,6-tetrahydropyridine-2-carbonitriles; the reaction with hydrobenzamide gives N-unsubstituted tetrahydropyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 209–211, February, 1988.     

Synthesis of 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes

The Michael addition of cyanothioacetamide to nitrostyrenes was investigated. Previously unknown 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes were obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1472–1477, October, 2007.     

Preparation of 3-hydroxy- and 3-methoxy-N-heteroaryl-2-methyl-4-pyridones

A number of new 3-hydroxy- and 3-methoxy-2-methyl-4-pyridones substituted on the nitrogen atom with selected heterocycles has been prepared. Novel chelating properties of the hydroxy-compounds are expected.     

Synthesis of N,6-diaryl-2-imino-4-methyl-3-cyano-1,2,3,6-tetrahydropyrimidine-5-carboxamides

Russian Journal of General Chemistry -     

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.     

Azaindole derivatives. 67. Synthesis of N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles

N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles have been synthesized from the respective 1-benzyl-4-methyl-5-cyano-6-chloro(and 6-hydroxy)-7-azaindoles. The effect of the 5-cyano group on the oxidation-reduction processes accompanying nucleophilic replacement of chlorine in 6-chloro-7-azaindoles by primary and secondary amines has been considered. 7-Azaindoline compounds were dehydrogenated by chloranil to N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles.For communication 66, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 91–96, January, 1986.     

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.     

The synthesis of annelated 3-cyano-2-pyridones

Annelated tricyclic 3-cyano-2-pyridones were synthesized from cyanoacetamide adducts using a thermal cyclization process which had previously been reported to afford an annelated pyrimidone product.     

Synthesis of 2-amino-3-cyano-4H-chromen-4-ylphosphonates and 2-amino-4H-chromenes catalyzed by tetramethylguanidine

Synthesis of 2-amino-4H-chromen-4-ylphosphonates and 2-amino-4H-chromenes has been accomplished by the reaction of salicylaldehyde, malononitrile, dialkyl/diphenylphosphites catalyzed by 1,1,3,3-tetramethylguanidine (TMG) under neat conditions at room temperature. The applicability of catalytic TMG for the synthesis of 2-amino-4H-chromenes also has been described. The mild reaction conditions, simple work-up procedure, and use of TMG as an inexpensive catalyst provides an economical protocol for the preparation of important phosphorus-containing compounds.