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 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-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 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 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.     

Synthesis and Crystal Structure of 4-（4-Chlorophenyl）-6-methyl-5-methoxy-caronyl-3,4-dihydropyrimidin-2（H）-one

1 INTRODUCTION Biginelli reaction is a three-component condensa-tion of ethyl acetoacetate, benzaldehyde and urea forthe synthesis of 3,4-dihydropyrimidin-2(1H)-ones(Scheme 1). The reaction can be carried out in aone-pot fashion in alcohol solution in t…     

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.     

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.     

1-(Pyrimidin-4-yl)pyrazol-5(4H)-one derivatives: I. Synthesis of 3-methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-pyrazol-5-ol and specificity of its Knoevenagel reaction

3-Methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-1H-pyrazol-5-ol available via cyclocondensation of 6-methyl-2-methylsulfanylpyrimidin-4-ylhydrazine with ethyl acetoacetate reacted with aromatic aldehydes to give two kinds of products, 4-arylmethylidene-5-oxo-4,5-dihydropyrazole and arylbis(5-hydroxypyrazol-4-yl)methane derivatives, depending on the substituent in the aromatic aldehyde.     

Über Dihydro-6-methyl- bzw.-6-styryl-4-phenyl-2(1H)-pyrimidinone (-thione) sowie Hexahydro-5-benzoyl- bzw.-cinnamoyl-4,7-diphenyl-2(1H)-chinazolinone (-thione)

Zusammenfassung Dihydro-6-methyl-4-phenyl-2 (1H)-pyrimidinone (-thione) (1) reagieren als -Methylalkenylharnstoffe bzw.-thioharnstoffe mit Säuren zu Hexahydro-4,4-methylendi-2(1H)-pyrimidinonen (-thionen) (3), mit Phenolen zu Tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinonen (-thionen) (2), mit Benzaldehyd zu 6-Styrylverbindungen (1 d, e, g) und mit ,-ungesättigten Ketonen zu Tetrahydro-2(1H)-chinazolinonen (7). Aus 1,5-Diphenyl-1,4-pentadien-3-on und Harnstoffen, Thioharnstoffen bzw. Ammonrhodanid entstehen Diphenyl-1,3,7,9-tetraazaspiro-5,5-undecan-2,8-dione (9) bzw. Hexahydrotriphenyl-6-cinnamoyl-2(1H)-chinazolinthione (10). Hexahydro-6-benzoyl-bzw.-6-cinnamoyl-2(1H)-chinazolinone (-thione) (10) bilden sich allgemein bei Einwirkung von ,-ungesättigten Ketonen auf Dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinone (-thione) (1 d, e, g).

---

Heterocycles, XXVII: Dihydro-6-methyl-(or-6-styryl-)-4-phenyl-2(1H)-pyrimidinones (-thiones); Hexahydro-5-benzoyl-(or-cinnamoyl-)-4,7-diphenyl-2(1H)-quinazolinones (-thiones)

Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinones (-thiones) (1) react as -methylalkenylureas (-thioureas) with acids to hexahydro-4.4-methylenedi-2(1H)-pyrimidinones (-thiones) (3), with phenols to tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinones (-thiones) (2), with benzaldehyde to 6-styryl compounds (1 d, e, g) and with ,-unsaturated ketones to tetrahydro-2(1H)-quinazolinones (7).On reacting 1.5-diphenyl-1.4-pentadien-3-one with ureas, thioureas or ammonium thiocyanate, the products formed are diphenyl-1.3.7.9-tetraazaspiro-5.5-undecane-2.8-diones (9) and hexahydrotriphenyl-6-cinnamoyl-2(1H)-quinazolinethiones (10), resp. Hexahydro-6-benzoyl- (or-6-cinnamoyl-)-2(1H)-quinazolinones (-thiones) (10) are formed generally by the action of ,-unsaturated ketones on dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinones (-thiones) (1 d, e, g).

     

2-甲基-4-羟基-6-苯基嘧啶和2-甲基-4-羟基-5-溴-6-苯基嘧啶的高效液相色谱法分离测定

采用ODS-C18色谱柱和紫外检测器,对2-甲基-4-羟基-6-苯基嘧啶和2-甲基-4-羟基-5-溴-6-苯基嘧啶的含量进行HPLC分离测定.以甲醇水=4555为流动相,紫外检测波长为237 nm,样品线性范围为0.001～0.1 mg/mL.2-甲基-4-羟基-6-苯基嘧啶的RSD为0.5%;2-甲基-4-羟基-5-溴-6-苯基嘧啶的RSD为1.0%.     

Synthesis and Crystal Structure of 3-Carbamoyl-6-methyl-5-phenylcarbamoyl-2-thioxo-1,2,3,4-tetrahydropyridine-4-spirocyclohexane

3-Carbamoyl-6-methyl-5-phenylcarbamoyl-2-thioxo-1,2,3,4-tetrahydropyridine-4-spirocyclohexane has been synthesized by the condensation of cyclohexylidenecyanothioacetamide with acetoacetanilide and piperidine. The structure of the product was established by X-ray structural analysis.     

Synthesis under Microwave Irradiation and Crystal Structure of 4-（3,4-Methylenedioxylphenyl）-6-methyl- 5-ethoxycaronyl-3,4-dihydropyrimidin-2（H）-one

1 INTRODUCTION Since Biginelli firstly reported the synthesis of 3,4-dihydropyrimidin-2(1H)-ones in 1893, this com- pound has been found to emerge as calcium channel blockers, antihypersive agents and a-antagonists[1]. Consequently, this Biginelli reacti…     

Synthesis and transformations of 6-amino-3,5-dicyano-4ethylpyridine-2(1H)-thione

The condensation of propionaldehyde with cyanothioacetamide gives 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione, which was used to obtain substituted 2-alkylthiopyridines, 2-ethylthio-6- ethylaminopyridine, and pyrazolo[3,4-b]pyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Science, 117913 Moscow. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1094–1098, August, 1996. Original article submitted March 4, 1996; revision submitted July 1, 1996.     

Synthesis and structure of 6-amino-3,5-dicyano-4-heptylpyridine-2(1H)-thione

Condensation of caprylic aldehyde with cyanothioacetamide taken in a ratio of 1:2 affords 6-amino-3,5-dicyano-4-heptylpyridine-2(1H)-thione. The structure of the thione was studied by X-ray structural analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–198, January, 1997.