Synthesis of Arylidene Derivatives of 1-Aryl-3H-pyrrol-2-ones

The aminolysis of 5-aryl-3-arylidene-3H-furan-2-ones by the action of aromatic amines leads to the formation of substituted amides of 4-oxo acids, the subsequent azacyclization of which in the presence of acetic anhydride leads to the formation of 1,5-diaryl-substituted 3-arylidene-3H-pyrrol-2-ones. The mechanism of the occurring and alternative transformations is discussed.     

Arylmethylene derivatives of 5-R-3H-furan-2-ones and N-aryl-5-R-3H-pyrrol-2-ones in reaction with acetylacetone

Reaction with acetylacetone in the series of 3-arylmethylene-substituted furan-2-ones and pyrrol-2-ones was studied. 8-R-4-Acyl-5-aryl-3-oxo-9-oxabicyclo[4.3.0]nona-1,7-dienes and N-tolyl-8-R-4-acyl-5-aryl-3-oxo-9-azabicyclo[4.3.0]nona-1,7-dienes were synthesized. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1457–1462, October, 2007.     

Reactivity of pyrrol-2-ones. (review)

Published data on the chemical transformations of pyrrol-2-ones are reviewed and analyzed. The extensive synthetic possibilities of compounds containing a pyrrolone ring in the synthesis of various heterocyclic compounds with complex structures are demonstrated. The reactions are arranged according to the reaction centers of the pyrrol-2-ones: The methylene unit, the C=C double bond, the electron-deficient carbon atom of the carbonyl group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1463, October, 2004.     

Reactions of 2-aryl-4-arylidene-4<Emphasis Type="Italic">H</Emphasis>-oxazol-5-ones with 3-amino-1,2,4-triazole, 5-aminotetrazole,and 2-aminobenzimidazole

The reactions of 3-amino-1,2,4-triazole, 5-aminotetrazole, and 2-aminobenzimidazole with 2-aryl-4-arylidene-4H-oxazol-5-ones (azlactones) were studied. The electron-releasing properties of the azole ring were demonstrated to influence the reaction pathway of azlactones with aminoazoles. The structures of the resulting compounds were established by ¹H and ¹³C NMR spectroscopy using spin-spin decoupling and the nuclear Overhauser effect.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2730–2733, December, 2004.     

Bromination of 5-Substituted 3H-Furan-2-ones and 3H-Pyrrol-2-ones

The bromination of 5-alkyl(aryl)-3H-furan-2-ones and 5-alkyl(aryl)-3H-pyrrol-2-ones and also their derivatives takes place at the ethylene bond with the formation of 4-monobromo derivatives. N-Phenyl-3H-pyrrol-2-ones are brominated simultaneously at the ethylene bond of the heterocycle and at the phenyl substituent at the nitrogen atom.     

Effective synthesis of 5-aryl-3-ethylidene-3H-pyrrol-2-ones

Substituted 5-aryl-3-ethylidene-3H-pyrrol-2-ones were synthesized by the reaction of the corresponding 4-aryl-4-oxobutanoic acids with ketones in the presence of aminating agents. The conditions of this reaction were developed with the use of both the conventional condensation technique and microwave activation. The structures of the reaction products were con-firmed by elemental analysis, IR spectroscopy, and ¹H NMR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 693–696, April, 2006.     

Heterophase N-aminomethylation of 5-arylidenepseudothiohydantoins by arylamines and aqueous formaldehyde in aromatic solvents: Effect of substituents in the heterocyclic substrate and the aryl amine on the efficiency of the process

We have obtained a series of 3-aryl-7-arylidene-3,4-dihydro-2H-[1,3]thiazolo[3,2-a][1,3,5]triazin-6(7H)-ones by means of heterophase aminomethylation of 2-amino-5-arylidene-1,3-thiazol-4(5H)-ones with aqueous formaldehyde and aromatic amines in benzene or toluene. We explain the effect of substituents in the heterocyclic substrate and the aryl amine on the efficiency of the process within a detailed scheme for one of the possible aminomethylation reaction routes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1095–1104, July, 2006.     

Reaction of 1-Aryl-3-methylpyrazol-5-ones with 2-Cyanoaryldiazonium Bisulfates

2-Cyanoaryldiazonium bisulfates, obtained by the action of nitrosyl sulfuric acid on isatin 3-hydrazone and its 5-bromo and 5-nitro derivatives, couple with 1-aryl-3-methylpyrazol-5-ones and form 4-arylhydrazones of 1-aryl-3-methylpyrazole-4,5-diones. It was established on the basis of data of IR, UV, and ¹H NMR spectra and of X-ray structural analysis that the coupling products exist in the hydrazone form stabilized by an intramolecular hydrogen bond.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 210–215, February, 2005.     

Heterocyclization of Derivatives of 4-Oxoalkanoic Acids to 1,5-Disubstituted Pyrrolin-2-ones

Conditions were developed for the synthesis and production of 1-aryl-5-alkyl(aryl)-3H- and 1-aryl-5-alkyl(aryl)-5H-pyrrolin-2-ones from the amides and esters of 4-oxoalkanoic acids. It was established that the yield and ratio of the 3H and 5H isomers depend on the substrate employed in the reaction.     

Easy formation of SNH products in reactions of indoles and pyrroles with 3-aryl-1,2,4-triazin-5(2H)-ones in the presence of tosyl chloride

The reactions of 3-aryl-1,2,4-triazin-5(2H)-ones with indoles and pyrroles in the presence of p-toluenesulfonyl chloride afforded 3-aryl-6-hetaryl-1,2,4-triazin-5(2H)-ones in high yields. The latter are products of the nucleophilic substitution of hydrogen.     

Unexpected Synthesis of Novel 3-Allyl-5-(arylidene)-2-thioxo-thiazolidin-4-ones in Reactions of 3-Allylrhodanine with 2-Arylidene-4-methyl-5-oxopyrazolidinium Ylides

Abstract

The reaction of 3-allylrhodanine with 2-arylidene-4-methyl-5-oxopyrazolidinium ylides proceeded unexpectedly to form novel 3-allyl-5-(arylidene)-2-thioxo-thiazolidin-4-ones 6a–k in good yields. All structures have been formulated on the basis of their spectral (IR, NMR, MS) data and elemental analyses. In addition, the structure of compound 6a was confirmed by means of x-ray crystallographic analysis.     

Synthesis of arylidene derivatives of N-unsubstituted pyrrolin-2-ones

5-Alkyl(aryl)-3-arylidene-3H-pyrrolin-2-ones were synthesized by ammonolysis of their O-heteroanalogs or by the reactions of 5-alkyl(aryl)-3H-pyrrolin-2-ones with aromatic aldehydes. The structures of the compounds obtained were confirmed by ¹H NMR spectra.     

Camps reaction for the synthesis of 3-RS-4-arylquinolin-2-ones

The replacement of the chlorine atom in 2-(chloroacetamido)benzophenones on treatment with RSH (R = Alk, Ar, Hetaryl) in the presence of MeONa is accompanied by intramolecular cyclization following the Camps reaction pattern to give 3-RS-4-arylquinolin-2-ones. Cleavage of 4-aryl-3-(benzoxazol-2-ylthio)quinolin-2-ones by morpholine has resulted in the corresponding 4-aryl-3-mercaptoquinolin-2-ones.     

Synthesis and structure of 3-arylidene and 3-hetarylidene-1,2-dihydro-3H-1,4-benzodiazepin-2-ones and their affinity toward CNS benzodiazepine receptors

The condensation of 5-aryl-7-bromo-1,2-dihydro-3H-1,4-benzodiazepin-2-ones with aromatic aldehydes gives 5-aryl-3-arylidene-and 5-aryl-7-bromo-3-hetarylidene-1,2-dihydro-3H-1,4-benzodiazepin-2-ones. X-ray diffraction structural analysis yielded the molecular and crystal structures of 7-bromo-3-(4′-methoxybenzylidene)-5-phenyl-1,2-dihydro-3H-1,4-diazepin-2-one and showed that this compound has cis configuration. Radioligand analysis was used to study the affinity of these products toward central nervous system and peripheral benzodiazepine receptors. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1225, August, 2007.     

The chemical behavior of 2-methylene-2,3-dihydro-3-furanones

Diphenylketene undergoes regioselective thermal [2+2]-cycloaddition to the heterocyclic C(3)=O carbonyl group of 5-aryl-2-methoxycarbonylmethylene-2,3-dihydrofuran-3-ones and 5-phenyl-2,3-dihydrofuran-2,3-dione to give the corresponding 3-diphenylmethylene derivatives of 2,3-dihydrofuran.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 331–334, February, 1995.     

Cycloaddition of 2-acylmethyl-1H-benzimidazoles to 4-arylidene-1,3-oxazol-5-ones

Cycloaddition of 2-phenacyl-1H-benzimidazole to 2-phenyl-or 2-methyl-4-arylidene-1,3-oxazol-5-ones occurs regioselectively to form the previously unknown N-(3-aryl-4-benzoyl-1-oxo-1,2,3,4-tetrahydropyrido[1,2-a]benzimidazol-2-yl)benz-and-acetamides. The analogous cycloaddition of the 2-acetonyl-1H-benzimidazole is complicated by prototropic isomerization and leads to the corresponding 1,2,3,5-tetrahydropyrido[1,2-a]benzimidazole. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 78, pp. 1008–1014, July, 2007.     

Synthesis of 5-Hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano[2,3-c]pyridin-2-ones and Their Esters

New 5-hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano-[2,3-c]pyridin-2-ones and their esters were synthesized. The structure of obtained compounds was determined through a complete ¹H NMR analysis.     

Cycloacylation of 3-oxo-3-R1-N-R2-propanethioamides by 3-aryl-2-propenoyl chlorides

The products of cyclocondensation of 3-oxo-3-R¹-N-R²-propanethioamides with 3-aryl-2-propenoyl chlorides in acetone in the presence of potassium carbonate are 5-acyl-1-aryl(alkyl)-4-aryl-6-thioxopiperidin-2-ones, 5-acyl-2-aryl-6-aryl(alkyl)amino-2,3-dihydro-4H-thiopyran-4-ones, and 2-acetonylidene-3,6-diaryl-5,6-dihydro-4H-1,3-thiazin-4-ones, the structure of which is proven by both spectral methods and chemical conversions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 623–628, April, 2006     

Convenient synthesis of pyrazolo[3,4-b]pyridin-3-ones and pyrazolo[3,4-b]pyridine-5-carbaldehyde using vinamidinium salts

An expedient method for the synthesis of 2-phenyl-5-aryl-2,3-dihydropyrazolo[3,4-b]pyridin-3-ones and 2-phenyl-3-oxo-2,3-dihydropyrazolo[3,4-b]pyridine-5-carbaldehyde in a single-step via condensation of vinamidinium salts with 3-amino-1-phenyl-2-pyrazolin-5-one is described.     

Synthesis of 2-aryl-5H-[1,3,4]-thiadiazolo[2,3-b]quinazolin-5-ones

3-Amino-2-thioxo-1,2,3,4-tetrahydroquinazolin-4-ones were converted into 2-aryl-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-ones on treatment with carboxylic acids and POCl₃. 3-Arylmethylidenamino-2-thioxo-1,2,3,4-tetrahydroquinazolin-4-ones also cyclized to 2-aryl-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-ones when oxidized with potassium chlorate in acetic acid, but on heating they were deaminated to give 2-thioxo-1,2,3,4-tetrahydroquinazolin-4-one and aryl nitriles. __________ Translated from Khimiya Geteotsiklicheskikh Soedinenii, No. 5, 787–791, May, 2006.