1,3,4,6-Tetracarbonyl Compounds: IV. Reaction of 3,4-Dihydroxy-2,4-hexadiene-1,6-diones with Hydrazine and Arylhydrazines

Reactions of 1,6-disubstituted 3,4-dihydroxy-2,4-hexadiene-1,6-diones with hydrazine hydrate or hydrochloride afforded heterocyclization products, 3,3'-bipyrazoles. The chemoselective reaction of 1,6-diaryl-3,4-dihydroxy-2,4-hexadiene-1,6-diones with arylhydrazines gave rise to 1,1',5,5'-tetraaryl-3,3'-bipyrazoles and 1,5-diaryl-3-aroylacetylpyrazoles. The specific structural features of the pyrazole derivatives obtained are discussed. Some pyrazoles show bacteriostatic and antileukemic activity.     

1,3,4,6-tetracarbonyl compounds. 3. synthesis, structural features, and antimicrobial activity of 1,6-diaryl-3,4-dihydroxy-2,4-hexadiene-1,6-diones

The Wittig reaction of 5-aryl-2,3-dihydro-2,3-furandiones with aroylmethylenetriphenylphosphoranes is regioselective and leads to the formation of 5-aryl-2-aroylmethylene-2,3-dihydro-3-furanones. In the presence of acid the products react with water, giving satisfactory yeilds of 1,6-diaryl-3,4-dihydroxy-2,4-hexadiene-1,6-diones. The latter were also obtained by the reaction of 2,3-furandiones with alkylnitroamines. The base-catalyzed condensation of 2,3-furandiones with acetophenones led to 1,6-diaryl-3,4-dihydroxy-2,4-hexadiene-1,6-diones, which exist in DMSO solution in equilibrium with the cyclic oxo tautomers —substituted 2-hydroxy-2,3-dihydro-3-furanones. Some of the synthesized compounds exhibit antimicrobial activity toward standard strains ofStaphylococcus aureus andEscherichia coli.For Communication 2, see [1].Perm Pharmaceutical Academy, Perm, Russia; e-mail: kvo@pi.ccl.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1466–1475, November, 1999.     

1,3,4,6-Tetracarbonyl Compounds: VI. Synthesis of 2-Substituted 6-Aryl-3,4-dihydroxy-6-oxo-2,4-hexadienoic Acid Esters and Amides

The Knoevenagel reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with ethyl cyanoacetate or malonodinitrile yields 2-substituted 6-aryl-3,4-dihydroxy-6-oxo-2,4-hexadienoic acid esters or amides which exhibit biological activity. The structure of the products is discussed, taking into account the structure of known 3,4-dihydroxy-6-oxo-2,4-hexadienoic acid esters and 1,6-diaryl-3,4-dihydroxy-2,4-hexadiene-1,6-diones.     

Reactions of Acylpyruvic Acids and 2,3-Dihydrofuran-2,3-diones with 2,3-Diaminopyridine

Acylpyruvic acids readily react with 2,3-diaminopyridine to form (Z)-3-acylmethylene-1H-3,4-di- hydropyrido[2,3-b]pyrazin-2-ones. 5-Aryl-2,3-dihydrofuran-2,3-diones which can be regarded as lactones derived from -enolized aroylpyruvic acids react with 2,3-diaminopyridine under mild conditions, yielding regioisomeric (Z)-2-aroylmethylene-4H-1,2-dihydropyrido[2,3-b]pyrazin-3-ones. The structure of the products and reaction chemoselectivity are discussed.     

Reaction of 3,4-dioxohexane-1,6-dioic acid esters with 2,4-dinitrophenylhydrazine

Reaction was studied of 3,4-dihydroxyhexa-2,4-diene-1,6-dioic acid esters with 2,4-dinitrophenylhydrazine that led to the formation of esters of (3E)-3-[2-(2,4-dinitrophenyl)-hydrazinylidene]-4-oxohexane-1,6-dioic and (3E,4E)-3,4-bis[2-(2,4-dinitrophenyl)hydrazinylidene]-hexane-1,6-dioic acids. The structural features of compounds synthesized were established from the data of IR and NMR spectra and X-ray diffraction (XRD) analysis.     

Reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with ketene acetals

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, p. 1567, November, 1991.     

Synthesis of polyenamines by vinylogous nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with diamines

Novel polyenamines with inherent viscosities in the 0.2–1.1 range were synthesized by the vinylogous, nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with aromatic and aliphatic diamines in polar aprotic solvents at room temperature. The most effective polymerization medium was hexamethylphosphoramide for preparing high-molecular-weight polymers from aromatic diamines. The dilute solutions showed a marked decrease in viscosity with time. The aromatic polyenamines began to lose weight around 200°C under thermogravimetric analysis in air and nitrogen.     

Five-membered 2,3-dioxoheterocycles. 28. Reaction of 5-aryl-2,3-dihydrofuran-2,3-diones with thioamides and thiosemicarbazides

The reaction of 5-aryl-2,3-dihydrofuran-2,3-diones (I) with thiocarbonyl compounds has been described only for thiourea. The products of this reaction are 3-aryl-5-phenacylidene-4-oxoimidazolidine-2-thiones [2]. It seemed of interest to study the conversion of the furandiones (I) with a wider range of thiocarbonyl compounds such as thioamides and thiosemicarbazides.For Communication 27 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1461–1464, November, 1992.     

Unusual Reaction of Sodium 1,6-Dioxo-2,4-alkadiene-3,4-diolates under Acid Hydrolysis Conditions

The reaction of sodium 1,6-dioxo-2,4-alkadiene-3,4-diolates with HCl solution afforded unexpected hydrolysis products, namely (2Z)-2-hydroxy-4-oxobut-2-enoic (2,4-dioxobutanoic) acid esters. The structural features of the synthesized compounds were discussed on the basis of IR, ¹H NMR spectroscopy, mass spectrometry and X-ray diffraction analysis data.     

Five-Membered 2,3-Dioxo Heterocycles: XLVII. Reaction of 5-Aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with Compounds Containing C = N and C≡N Bonds

Thermal decarbonylation of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones gives rise to intermediate aroyl(phenyl)ketenes which react with nonactivated Schiff bases, N,N'-dicyclohexylcarbodiimide, and p-di-methylaminobenzonitrile according to the [4 + 2]-cycloaddition pattern with formation of 6-aryl-5-phenyl-4H-1,3-oxazin-4-ones. Reactions of 5-aryl-4-phenyl-2,3-dihydrofuran-2,3-diones with activated Schiff bases at a temperature below the thermolysis temperature lead to 4-aroyl-4-phenyltetrahydropyrrole-2,3-diones.     

Reaction of 3-aminoquinoline-2,4-diones with nitrourea. Synthetic route to novel 3-ureidoquinoline-2,4-diones and imidazo[4,5-c]quinoline-2,4-diones

1-Unsubstituted 3-alkyl/aryl-3-amino-1H,3H-quinoline-2,4-diones react with 1-substituted and 1,1-disubstituted ureas in boiling acetic acid to give 2,6-dihydro-imidazo[1,5-c]quinazoline-3,5-diones. In contrast, the reaction of these amines with nitrourea in dioxane affords novel 3-alkyl/aryl-3-ureido-1H,3H-quinoline-2,4-diones or 9b-hydroxy-3a-alkyl/aryl-3,3a,5,9b-tetrahydro-1H-imidazo[4,5-c]quinoline-2,4-diones, which can smoothly be dehydrated to 3a-alkyl/aryl-3,3a-dihydro-5H-imidazo[4,5-c]quinoline-2,4-diones. All three types of products can be converted to 2,6-dihydro-imidazo[1,5-c]quinazoline-3,5-diones by refluxing in acetic acid.     

Structure of Reaction Products of 1,3,4,6-Tetracarbonyl Compounds with o-Aminothiophenol. Synthesis of 3-aryl-1-(1,3-benzothiazol-2-yl)-3-hydroxyprop-2-en-1-ones

Russian Journal of Organic Chemistry - 1,6-Diarylhexane-1,3,4,6-tetraones react with o-aminothiophenol forming 3-aryl-1-(1,3-benzothiazol-2-yl)-3-hydroxyprop-2-en-1-ones.     

Reaction of Aliphatic Diazo Compounds with Dinitrogen Trioxide. A Facile route to 3,4-Disubstituted 1,2,5-Oxadiazole-2-oxides(Furoxans)

As part of our continuing studies¹of the chemistry of diazo compounds, we have investigated the reaction of α-diazosulfones, α-diazoketones and ethyl diazoacetate with dinitrogen trioxide. When a solution of the diazo compound is allowed to react at 0–5° with excess n₂O₃ ² in CH₂Cl₂, and almost instantaneous evolution of a gas (presumably nitrogen) is observed. Work-up afforded 3,4–disubstituted furoxans (I–VII, see Table) in good Yields.     

Five-membered 2,3-dioxo heterocycles. 21. Reaction of 1,5-diaryl-4-ethoxycarbonyl-tetrahydropyrrole-2,3-diones with 2-aminopyridine

The reaction of 2-aminopyridine with 1,5-diaryl-4-ethoxycarbonyltetrahydropyrrole-2,3-diones gave 11 complexes, which are converted to N-(2-pyridyl)-1,5-diaryl-3-hydroxy-2-oxo-2,5-dihydropyrrole-4-carboxamides when they are heated above their melting points without a solvent. The character of the hydrogen bonds in the complexes obtained is discussed.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–36, January, 1992.     

Three-Component Reaction of 1H-Pyrrole-2,3-diones with Malononitrile and Phthalhydrazide

Russian Journal of Organic Chemistry - Base-catalyzed three-component condensation of ethyl 4,5-dioxo-4,5-dihydro-1H-pyrrole-3-carbox­ylates with malononitrile and phthalhydrazide afforded...     

The Reaction of 1,2:3,4-Diepoxy-2,3-dimethylbutane with Nucleophiles

To find out whether the 1,4-addition to 1,2:3,4-diepoxides, which so far has been observed only once, is of a more general character, we investigated the reaction of a variety of O-, C-, N-, and S-nucleophiles with the model compound 1,2:3,4-diepoxy-2,3-dimethylbutane (Scheme 4). In several cases, 1,4-addition products could, indeed, be observed besides the expected 1,2-adducts (Table).     

Multicomponent Synthesis of 2,3-Dihydrochromeno[4,3-d]pyrazolo[3,4-b]pyridine-1,6-diones: A Novel Heterocyclic Scaffold with Antibacterial Activity

A multicomponent reaction of 3-aminopyrazol-5-ones with substituted salicylic aldehydes and acetylacetic ester leading to the formation of novel 2,3-dihydrochromeno[4,3-d]pyrazolo[3,4-b]pyridine-1,6-diones was discovered. The elucidation of the reaction scope revealed that 5-aminopyrazoles, 3-amino-1,2,4-triazoles and 6-aminouracil could be used as the heterocyclic amine component. Selected heterocyclic products were found to possess notable antibacterial activities.     

Reactions with pyrrolidine-2,4-diones,I. New synthesis of pyrano[2,3-c]pyrrole and pyrrolo[3,4-b]pyridine systems

The synthesis of some substituted 4-hydroxy-2,5,6,7-tetrahydro-pyrano[2,3-c]pyrrole-2,5-diones (5) and 4-hydroxy-1,2,6,7-tetrahydro-5H-pyrrolo[3,4-b]pyridine-2,5-diones (6) by reacting 1,5-diaryl-pyrrolidine-2,4-diones (1) and 1,5-diaryl-1,5-dihydro-4-amino-2H-pyrrol-2-ones (3) with bis-2,4,6-trichlorophenyl malonates (4) is described.Dedicated to Prof. Dr. Dr. h. c.O. Kratky, Graz, on the occasion of his 80th birthday.