3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

Chemistry of 3-hetarylcoumarins. 2. 3-(2-thiazolyl)coumarins

3-(2-Thiazolyl)coumarins were obtained by the reaction of substituted salicylaldehydes with 2-thiazolylacetonitriles. Methylation, acylation, and aminomethylation were studied for the 7-hydroxy-substituted products.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1632–1644, November, 2004.     

Synthesis of 3,3-dialkyl-1-(3-pyridyl)-3,4-dihydroisoquinolines

It has been shown that the reaction of dialkylbenzylcarbinols with 3-cyano-2-pyridones and 2-chloro-3-cyanopyridines gives the corresponding 3,3-dialkyl-1-(3-pyridyl)-3,4-dihydroisoquinolines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1208–1212, August, 2007.     

Plant Coumarins. 2. Beckmann Rearrangement of Oreoselone <Emphasis Type="Italic">E</Emphasis>- and <Emphasis Type="Italic">Z</Emphasis>-Oximes

Oximation of oreoselone to produce a mixture the E- and Z-oximes was investigated. The crystal and molecular structures of oreoselone Z-oxime and the Beckmann rearrangement product of oreoselone E- or Z-oximes and PCl₅, 7-(1-chloro-2-methylpropoxy)-2-oxo-2H-1-benzopyran-6-carbonitrile, were established by XSA. Hydrolysis of the latter produced 7-hydroxy-2-oxo-2H-1-benzopyran-6-carbonitrile. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 541–545, November–December, 2005.     

Synthesis and properties of 4-chloromethyl-6-hydroxy-coumarins and 4-(2-benzofuryl)-6-hydroxycoumarins

New 4-chloromethyl-6-hydroxycoumarins have been obtained by the condensation of hydroquinone derivatives with 4-chloroacetoacetic ester, and have been used for the synthesis of 4-(2-benzofuryl)-6-hydroxycoumarins. Alkylation and acylation of the phenolic hydroxyl of the synthesized 4-(2-benzo-furyl)coumarins have been investigated. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 361–369, March, 2009.     

Synthesis and structure of new oxoindoles

The synthesis and study of the structure of new oxoindoles has been carried out. The molecular and crystal structure, and the stereochemistry atom of C(3) of 1,2-diacetyl-5′-phenyl(2′,4′ dihydrospiro[3H-indol-3,3′-[3H]pyrazol]-2-(1H)-one have been established by X-ray crystallography. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, 374–382, March 2007.     

Reaction of imidazole series aldeydes with bis[2-(2-pyridyl)ethyl]-phosphine chalcogenides: Synthesis of polyfunctional heterocyclic systems

The nucleophilic addition of bis[2-(2-pyridyl)ethyl]phosphine sulfide and bis[2-(2-pyridyl)-ethyl]phosphine selenide to 2-formyl-1-organylimidazoles and benzimidazoles occurs efficiently without catalysis at room temperature to give functionalized heterocyclic compounds containing imidazole, benzimidazole, and pyridine rings and also chalcogenophosphoryl and hydroxyl groups. Dedicated to Professor A. Pozharskii on his 70th jubilee Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1669–1675, November, 2008.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

An unexpected reaction of 2-(cyclopent-2-enyl)aniline hydrochloride with dimethyldioxirane

An unusual direction of the reaction of 2-(cyclopent-2-enyl)aniline hydrochloride with dimethyldioxirane was found: the formation of two isomeric products,viz., 3- and 6-chloro-2-(cyclopent-2-enyl)anilines, was observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1654–1655, August, 1998.     

1-( p -Fluorophenyl)-2-(2′-pyridyl)ethanol and 1-( p -fluorophenyl)-2-(2′-pyridyl)ethene obtained from the condensation reaction of 2-picoline and p -fluorophenylaldehyde under catalyst-and solvent-free conditions

The novel intermediate 1-(p-fluorophenyl)-2-(2′-pyridyl)ethanol or 2-[2′-(1-hydroxy-1-(p-fluorophenyl)ethyl]pyridine and the corresponding novel dehydration compound 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene or 2-[p-fluorophenylvinyl]pyridine were obtained from the condensation reaction of p-fluorophenylaldehyde and 2-picoline under catalyst-and solvent-free conditions. The intermediate 1-(p-fluorophenyl)-2-(2′-pyridyl)ethanol was obtained at 42 h reaction time and temperature of 120°C, respectively. ¹H-NMR, IR spectroscopic data of the 1-(p-fluorophenyl)-2-(2-pyridyl)ethanol clearly showed the presence of the-CH₂-CHOH-group. The compound was obtained as a white powder with m.p. 121–122°C and a yield of 8%. For 1-(p-fluorophenyl)-2-(2-pyridyl)ethene, the reaction conditions were similar, but the reaction temperature was increased to yield the double bond in the 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene. At the reaction temperature of 140°C, the compound was a slightly brown powder with a m.p. of 78°C and yield of 18%. ¹H-NMR, IR spectroscopic data for the 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene showed the presence of a double bond in trans configuration (-CH=CH-), characteristic of a styrylpyridine.     

Alternative products in one-pot reaction of benzylidenemalononitrile,N-methyl-2-thiocarbamoylacetamide,and ω-bromoacetophenone

N-Methyl-2-benzoylmethylsulfanyl-4-phenylnicotinamide and N-methyl-2-(4-phenyl-1,3-thiazol-2-yl)-acetamide have been obtained as alternative products to the desired N-methyl-2,3-dihydro-7H-thiazolo[3,2-a]pyridine-8-carboxamide by a one-pot cyclocondensation of benzylidenemalononitrile, N-methyl-2-thiocarbamoylacetamide, piperidine, and ω-bromoacetophenone. 2-Amino-1-methyl-6-oxo-4-phenyl-5-(4-phenyl-1,3-thiazol-2-yl)-1,6-dihydropyridine-3-carbonitrile has been obtained as main product by treatment of benzylidenemalononitrile with N-methyl-2-(1,3-thiazol-2-yl)acetamide. Dedicated to Professor I. Kalvinsh on his 60th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 777–781, May, 2007.     

Oxidative reactions of azines

Oxidative coupling of 1-alkyl(benzyl)-4-(γ-pyridyl)-1,2,5,6-tetrahydropyridines with acetone in the presence of KMnO₄ follows two pathways and yields both 1-R-2-(acetylmethylene)tetrahydropyridines and 1-R-3,4-dihydroxypiperidin-2-ones. When acetonitrile is used instead of acetone, the reaction under similar conditions occurs as selective ketodihydroxylation of the starting piperideines yielding 1-R-3,4-dihydroxy-4-(γ-pyridyl)piperidin-2-ones. The molecular and crystal structures of one of these products (R=Et) was studied by X-ray diffraction analysis. For part 4, see Ref. 1 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2020–2023, November, 1997.     

Synthesis of novel N2-adamantyl derivatives of 2-amino-6-methyl-4(3H)-pyrimidinone as potential activators of tumor necrosis factor (TNF) release

A method has been developed for the synthesis of N²-adamantyl-2-amino-6-methyl-4(3H)-pyrimidinones based on the reaction of (adamant-1-yl)alkylamine with 2-(ethylsulfanyl)-6-methyl-4(3H)-pyrimidinone which can lead to the corresponding derivatives in which the exocyclic nitrogen atom and the adamantyl radical are separated by a hydrocarbon fragment. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1541–1544, October, 2006.     

Products from condensation of 1-(3(4)-acetylphenyl)-4-carboxy-2-pyrrolidinones with <Emphasis Type="Italic">o</Emphasis>-phenylenediamine and their properties

2-Substituted benzimidazoles were synthesized by the reaction of 1-(3(4)-acetylphenyl)-4-carboxy-2-pyrrolidinones with o-phenylenediamine. Their reactions with sodium hydroxide and hydrazine and some of their chemical characteristics were investigated. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp.1625–1630, November, 2007.     

Components of the heartwood of <Emphasis Type="Italic">Populus euphratica</Emphasis> from an ancient tomb

To probe the organic constituents of over 2000-year-preserved Populus euphratica found in an ancient tomb, a chemical investigation was undertaken, which led to the isolation of a new compound, 2-(4′-hydroxy-3′-methoxyphenyl)-2-oxoacetamide (1), together with 12 known compounds (2–13) by column chromatography. Their structures were elucidated on the basis of spectroscopic evidence. It is the first time that compounds 2–13 were isolated from this plant. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 7–9, January–February, 2008.     

Synthesis of 2-[2-(5-phenyl-1,2,4-oxadiazol-3-yl)-ethyl]benzimidazole and its x-ray analysis

Cyclization of O-benzoyl-2-(benzimidazol-1-yl)propioamidoxime under different temperature conditions gave 2-[2-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl]benzimidazole whose structure has been determined by X-ray analysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1057–1061, July, 2006.     

Investigation of 2-[2-(4-Methoxy-phenylamino)-vinyl]-1,3,3-trimethyl-3H-indolium Chloride as a New Reagent for the Determination of Chromium(VI)

 The complex formation and extraction of chromium(VI) with 2-[2-(4-methoxy-phenylamino)-vinyl]-1,3,3-trimethyl-3H-indolium chloride reagent was studied by means of spectrophotometry. The influence of medium acidity, the concentration of chloride ions and dye reagent, the nature of the extractant and some other factors (time of extraction, stability of color, interference, etc.) on the absorbance of colored extracts were studied. The optimum conditions were found to be 0.02–0.1 M H₂SO₄, 1.0–1.5 M NaCl, (2.0–2.5) × 10⁻⁴ M of reagent. The absorbance of the colored extracts obeys Beer’s Law in the range of 0.26–7.28 mg L⁻¹. The procedure of Cr(VI) extraction and spectrophotometric determination was examined. Author for correspondence. E-mail: andruch@kosice.upjs.sk Received November 19, 2002; accepted March 10, 2003 Published online June 13, 2003     

Chelate synthesis of 2,2′-bipyridin-4-one

A method for the synthesis of 2,2′-bipyridin-4-one from 4-amino-4-(2-pyridyl)-but-3-en-2-onevia its diphenylboron, chelates was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2071–2073, November, 1997.     

Reactions of 5-[3-(trifluoromethyl)-phenyl]furan-2-carbaldehyde

The Knoevenagel condensations of 5-[3-(trifluoromethyl)phenyl]furan-2-carbaldehyde with seven compounds containing an active methyl or methylene group have been studied. The compounds used were: methyl 2-cyanoacetate, malononitrile, 2-furylacetonitrile, acetophenone, 2-thioxo-1,3-thiazolidin-4-one (rhodanine), 5,5-dimethylcyclohexane-1,3-dione (dimedone), and methyl 2-azidoacetate. The effect of microwave irradiation on the condensation reactions was studied and compared with “’classical”’ conditions. Thermolysis of methyl 2-azido-3-{5-[3-(trifluoromethyl)phenyl]-2-furyl}propenoate afforded methyl 2-[3-(trifluoromethyl)phenyl)]-4H-furo[3,2-b]pyrrole-5-carboxylate. (2E)-3-{ 5-[3-(Trifluoromethyl)phenyl]-2-furyl}propenoic acid was converted to the corresponding azide, which was cyclized on heating into 2-[3-(trifluoromethyl)phenyl)]-4,5-dihydrofuro[3,2-c]pyridin-4-one. The latter after successive action of POCl₃ and NH₂NH₂-Pd/C gave 2-[3-(trifluoromethyl)-phenyl]furo[3,2-c]pyridine. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–831, June, 2006.     

Synthesis and properties ofN-[1-hydroxyimino-2-methyl-1-(2-pyridyl)prop-2-yl]hydroxylamine and heterocyclic derivatives based on it

N-[1-Hydroxyimino-2-methyl-1-(2-pyridyl)prop-2-yl]hydroxylamine, a new representative of the series of α-hydroxylamino oximes, was synthesized. Based on this compounds, 3-imidazoline 3-oxide and 2-imidazoline 3-oxide derivatives, were obtained, and some of their chemical properties were investigated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 131–136, January, 1997.