4-Functionally Substituted 3-Heterylpyrazoles: IV. 1-Phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyrazolines

3-Aryl(heteryl)-4-formylpyrazoles in condensation with methyl aryl(heteryl) ketones afforded 1-aryl(heteryl)-3-[3-aryl(heteryl)-4-pyrazolyl]propenones. The latter reacted with phenylhydrazine yielding 1-phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyrazolines.     

4-Functionally Substituted 3-Heterylpyrazoles: VIII. 3-Aryl(heteryl)-4-hydroxyl(chloro)methylpyrazoles

3-Aryl(heteryl)pyrazole-4-carbaldehydes were reduced with sodium tetrahydridoborate under mild conditions to give 3-aryl(heteryl)-4-hydroxymethylpyrazoles which were converted into the corresponding 4-chloromethyl derivatives by treatment with thionyl chloride. The subsequent reaction with triphenylphos- phine led to formation of triphenyl(4-pyrazolylmethyl)phosphonium chlorides, and Wittig reaction of the latter with aromatic or heteroaromatic aldehydes yielded 4-[2-aryl(heteryl)ethenyl]pyrazoles.     

Functionally Substituted 3-Heterylpyrazoles: XI. 3-[3-Aryl(heteryl)pyrazol-4-yl]propenoic and Propanoic acids

3-Aryl(heteryl)-4-formylpyrazoles by condensation with malonic acid furnish 3-[3-aryl(heteryl)- pyrazol-4-yl]propenoic acids that in the presence of Raney nickel are reduced by hydrazine hydrate to 3-[3-aryl(heteryl)pyrazol-4-yl]propanoic acids. The successive conversion of both type acids into the corresponding acyl chlorides, esters, and amides was performed.     

4-Functionally-substituted 3-Heterylpyrazoles: XV. 3-Aryl(heteryl)-1-phenyl-4-pyrazolylmethylamines and Heterocumulenes Obtained Therefrom

By reduction of 3-aryl(heteryl)-1-phenyl-4-azidomethyl-pyrazoles in the presence of Raney nickel or by hydrazinolysis of N-[3-aryl(heteryl)-1-phenyl-4-pyrazolylmethyl]phthalimides 4-pyrazolylmethylamines were obtained that in reaction with bis(trichloromethyl) carbonate afforded 3-aryl-(heteryl)-1-phenyl-4-pyrazolylmethyl isocyanates, and with carbon disulfide furnished 3-aryl-(heteryl)-1-phenyl-4-pyrazolylmethyl isothiocyanates.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 247–251.Original Russian Text Copyright © 2005 by Bratenko, Panimarchuk, Mel’nichenko, Vovk.     

4-Functionally Substituted 3-Heterylpyrazoles: IV. Benzylamino[3-aryl(heteryl)-4-pyrazolyl]methylphosphonic Acids

Derivatives of N-benzyl[3-aryl(heteryl)-4-pyrazolyl]methanimines react with diethyl phosphite to afford diethyl benzylamino[3-aryl(heteryl)-4-pyrazolyl]-4-methylphosphonates that on hydrolysis with 18% hydrochloric acid yield the corresponding aminophosphonic acids.     

4-Functionally Substituted 3-Heterylpyrazoles: XIII. 3-Aryl(heteryl)-4-(4-pyrazolyl)-1,2,3,4-tetrahydropyrimidin-2-ones(thiones)

Cyclocondesation of 3-aryl(heteryl)pyrazole-4-carbaldehydes with ethyl acetoacetate and urea (thiourea) in the presence of FeCl₃ · 6H₂O afforded 3-aryl(heteryl)-4-(4-pyrazolyl)-1,2,3,4-tetrahydropyrimidin-2-ones(thiones).__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 97–98.Original Russian Text Copyright © 2005 by Bratenko, Chornous, Vovk.     

4-Functionally Substituted 3-Heterylpyrazoles: III. 3-Aryl(heteryl)pyrazole-4-carboxylic Acids and Their Derivatives

3-Aryl(heteryl)-4-formylpyrazoles were cleanly oxidized by potassium permanganate in water-pyridine medium to afford in high yield 3-aryl(heteryl)pyrazole-4-carboxylic acids, that were further converted into the corresponding chlorides and amides.     

4-Functionally Substituted 3-Heterylpyrazoles: VII. 3-Aryl(heteryl)-1-phenyl-4-pyrazolecarbonyl Isothiocyanates

3-Aryl(heteryl)-1-phenyl-4-pyrazolecarbonyl isothiocyanates were synthesized by treatment of 3-aryl(heteryl)-1-phenyl-4-pyrazolecarbonyl chlorides with lead, sodium, or ammonium thiocyanate. Their reactions with amines, hydrazines, and acylhydrazines gave the corresponding thioureas and thiosemi- carbazides.     

4-Functionally Substituted 3-Heterylpyrazoles: XIV. <Emphasis Type="Italic">N</Emphasis>-Benzyl-<Emphasis Type="Italic">N</Emphasis>-[3-aryl(heteryl)-4-pyrazolylmethylene]amines and Their Derivatives

Reduction with sodium tetrahydridoborate of Schiff bases derived from 3-aryl(heteryl)pyrazole-4-carbaldehydes and benzylamines gave N-benzyl-N-[3-aryl(heteryl)-4-pyrazolylmethylene]amines which were acylated with benzoyl chloride and succinic and maleic anhydrides to obtain the corresponding amides. Treatment of the title compounds with phenyl isothiocyanate afforded substituted thioureas.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 98–103.Original Russian Text Copyright © 2005 by Bratenko, Panimarchuk, Chornous, Vovk.     

Synthesis of aryl- and heteryl-containing gem-acylnitrocyclohexenes

Reactions of 2-aryl(heteryl)-1-acetyl(benzoyl)-1-nitroethenes with 2,3-dimethyl-1,3-butadiene led to the formation of products of [4+2]-cycloaddition, 1-acyl-6-aryl(heteryl)-3,4-dimethyl-1-nitro-3-cyclohexenes. Their structure was proved by IR and ¹H NMR spectroscopy.     

1H, 13C, 15N and 19F NMR study of acetylation products of heterocyclic thiosemicarbazones

Novel 2-acetylamino-4-acetyl-5-aryl(heteryl)-1,3,4-thiadiazolines, 2-acetylamino-5-aryl(heteryl)-1,3,4-thiadiazoles, and some of their salts were prepared and studied by multinuclear 1H, 13C, 15N, 19F and 2D NMR spectroscopy. The acetylation of thiosemicarbazones is accompanied by ring closure to form the corresponding 1,3,4-thiadiazolines and 1,3,4-thiadiazoles. 15N NMR spectroscopy is a unique method for the identification of thiadiazole pyridinium salts.     

N-Substituted 3-methoxycarbonyl-4-phenyl-2-pyrrolidones in reactions with nitroethenes

N-Substituted 3-methoxycarbonyl-4-phenyl-2-pyrrolidones react with 2-aryl(heteryl)-1-nitroethenes as typical CH-acids to give nucleophilic addition products. The structure of compounds obtained was studied by IR, ¹H and ¹³C NMR spectroscopy using HOESY experiment.     

Transformation of 4-aryl(heteryl)-2,6-diamino-3,5-dicyano-4H-thiopyrans into substituted acrylonitriles, 1,4-dihydropyridines, 2,3,4,7-tetrahydrothiazolo[3,2-a]pyridine, and 4,7-dihydrothieno[2,3-b]pyridine

Cross-recyclization of 4-aryl(heteryl)-2,6-diamino-3,5-dicyano-4H-thiopyrans with α-bromoketones or alkyl halides formed substituted 3-aryl-2-(4-R-thiazol-2-yl)acrylonitriles, 2-alkylsulfanyl-1,4-dihydropyridines, 2,3,4,7-tetrahydrothiazolo[3,2-a]pyridine, and 4,7-dihydrothieno[2,3-b]pyridine.     

Synthesis of 1H-pyrazolo[3,4-c]isoquinolin-1-ones by the condensation of cyclohexanone derivatives with 3-amino-1-phenyl-1H-pyrazol-5(4H)-one

The synthesis of 1H-pyrazolo[3,4-c]isoquinolin-1-ones was carried out by reacting 3-aryl(heteryl)-2,4-diacetyl-5-hydroxy-5-methylcyclohexanones with 3-amino-1-phenyl-1H-pyrazol-5(4H)-one. The structure of the 7-acetyl-2,4,6,7,8,9-hexahydro-8-hydroxy-5,8-dimethyl-2-phenyl-6-(fur-2-yl)-1H-pyrazolo[3,4-c]isoquinolin-1-one obtained was proved by X-ray diffraction analysis.     

2-R-5-Ar(Het)-5,6-dihydro-7H-[1,2,4]triazolo[5,1-b][1,3]thiazin-7-ones

A novel method for synthesis of 2-R-5-Ar(Het)-5,6-dihydro-7H-[1,2,4]triazolo[5,1-b][1,3]thiazin-7-ones by condensation of 3-R-4,5-dihydro-1H-1,2,4-triazole-5-thiones with 3-aryl(heteryl)-2-propenoyl chlorides is proposed.     

Synthesis of new methyl derivatives of aza-and diazaphenanthrene

By condensation of acetone with 2-naphthylamine and 3-(4-fluorophenyl)-1H-pyrazole-4-, pyridine-3-, quinoline-2-, quinoline-6-carbaldehyde and 4-(2-fluorobenzyloxy)benzaldehyde new 3-aryl(heteryl)-1-methylbenzo[f]quinolines were synthesized. Reactions of acetone with 6-quinolylamine and aromatic aldehydes provided 3-aryl-1-methyl-4,7-phenanthrolines. Intermediate reaction products were isolated: 4-phenyl-or (3-pyridyl)-4-(2-naphthylamino or 6-quinolylamino)butan-2-ones.     

Facile one pot multicomponent synthesis of novel 4-(benzofuran-2-yl)-2-(3-(aryl/heteryl)-5-(aryl/heteryl)-4,5-dihydro-1H-pyrazol-1yl)thiazole derivatives

An efficient base catalyzed one pot multicomponent reaction of aryl/hetryl chalcones, thiosemicarbazide and 1-(benzofuran-2-yl)-2-bromoethan-1-one was developed to synthesize the novel 4-(benzofuran-2-yl)-2-(3-(aryl/heteryl)-5-(aryl/heteryl)-4,5-dihydro-1H-pyrazol-1yl)thiazole derivatives.     

Synthesis of 5-Aryl(heteryl)-1-hydroxyethyl-4-(furyl-2-carbonyl)-3-hydroxy-3-pyrroline-2-ones

5-Aryl(heteryl)-1-hydroxyethyl-4-(furyl-2-carbonyl)-3-hydroxy-3-pyrroline-2-ones were synthesized via reactions of methyl ester of furyl-2-carbonylpyruvic acid with a mixture of aromatic or heterocyclic aldehyde and ethanolamine in dioxane. Antibacterial and antifungal activities of the synthesized compounds was studied.     

Synthesis and structure of nitroethylpyrrolidone carboxylates

3-Methoxycarbonyl-4-phenyl- and 4-(3-pyridyl)-2-pyrrolidones react with 2-aryl(heteryl)-1-nitroethenes to form C³-adducts as one or two diastereomers. Their structure was characterized by the IR, ¹H, and ¹³C NMR spectroscopy, using the two-dimensional correlation spectroscopy.     

Synthesis of 7-acetyl-2,3,5,6,7,8-hexahydro-6-hydroxy-1,6-dimethyl-3-thioxo-8-phenyl(heteryl)isoquinoline-4-carbonitriles Based on 2,4-Diacetyl-5-hydroxy-5-methyl-3-phenyl(heteryl)cyclohexanones

7-Acetyl-2,3,5,6,7,8-hexahydro-6-hydroxy-1,6-dimethyl-3-thioxo-8-phenyl(heteryl)isoquinoline-4-carbonitriles were obtained by reaction of 2,4-diacetyl-5-hydroxy-5-methyl-3-phenyl(heteryl)cyclohexanones with cyanothioacetamide. Structure of 7-acetyl-5,6,7,8-tetrahydro-6-hydroxy-1,6-dimethyl-3-methylthio-8-phenylisoquinoline-4-carbonitrile was proved by X-ray diffraction method.