[4+2]-Cycloaddition of 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5-tetrazines with alkenes

A number of 1,4-dihydropyridazines and pyridazines were prepared by the Diels-Alder reaction with an inverse electron demand from cyclic heterodiene systems, 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5-tetrazines, and some enamines as well as from 4-vinylpyridine, butyl vinyl ether, phenylacetylene, and acrylamide. The reaction of 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine with styrene afforded 4,5-dihydropyridazine, which was readily oxidized by atmospheric oxygen to form the corresponding pyridazine. Electron-withdrawing substituents (Br or Cl) in the pyrazole rings accelerate [4+2]-cycloaddition. When heated, 1,4-dihydropyridazines, which were synthesized from tetrazines and enamines, eliminated amine to give pyridazines. The reactivities of tetrazines were evaluated by quantum-chemical methods. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 354–360, February, 2000.     

Protonation of 1,2,4-triazine 4-oxides

The basicity of some 1,2,4-triazine 4-oxides was estimated on a quantitative level, and their probable protonation patterns were ascertained. The dissociation constants of mono- and diprotonated 3-R-6-phenyl-1,2,4-triazine 4-oxides in aqueous buffer solutions and aqueous sulfuric acid solutions were determined (6-phenyl-1,2,4-triazine 4-oxide: $pK_{BH^ + } = 1.1$ , $pK_{BH^{2 + } } = - 6.02$ ). According to the results of DFT calculations (B3LYP/6-311**) and spectral data, first protonation of 1,2,4-triazine 4-oxides involves the N¹ nitrogen atom, and the second proton adds to the N-oxide oxygen atom.     

Behavior of nanosized tungsten oxide bronzes produced by high-temperature electrolysis in model processes of desulfurization of petroleum products

Tungsten oxide bronzes were produced by an original method of high-temperature electrochemical deposition. Their catalytic properties in a model process of desulfurization of petroleum products-benzothiophene peroxidation were studied. The effect of the particle size on the catalytic and catalase activity of samples was shown.     

Regioselectivity of Nucleophilic Attack on the Reactions of 1,2,4-Triazine 4-Oxides with Certain C-Nucleophiles

The addition of CH-active compounds to 6-aryl-1,2,4-triazine 4-oxide is reversible and occurs under conditions of kinetic control at position 5 of the heterocycle to form cyclic C(5)-^H adducts. Under conditions of thermodynamic control the nucleophilic attack is directed to position 3 of the heterocycle and is accompanied by its opening to form the more stable open chain addition products. Attack of ethylmagnesium bromide is directed exclusively to the 5 position of the 6-aryl-1,2,4-triazine 4-oxides as a result of the irreversibility of the given reaction.     

Cyclization of N-alkylazinium cations with bifunctional nucleophiles. 15. Isomerization of thiazolo[4,5-b]quinoxalines in the presence of acids

4-Alkyl-2-phenyl-3a,4,9,9a-tetrahydrothiazolo[4,5-b]quinoxalines undergo isomerization in chloroform in the presence of acids to the regioisomeric (with respect to them) 9-alkyl-substituted derivatives. Under the same conditions 2,4-dimethyl-3a,4-9,9a-tetrahydrothiazolo [4,5-b]quinoxaline undergoes isomerization to 4-methyl-1H-2,3,3a,4,9,9a-hexahydropyrrolo[2,3-b]quinoxaline-2-thione. It was demonstrated by means of deuterium labels that in both cases the isomerization proceeds through a step involving dissociation to a quinoxalinium cation and the corresponding thioamide.See [1] for Communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 396–403, March, 1985.     

Mass spectrometry of nitrogenous heterocycles. 1. Mass spectrometric evaluation of stability of tetrahydropyrazines annelated to five- and six-membered heterocycles

Based on a study of electron impact mass spectra of a large number of tetrahydropyrazines, which are joined to five- and six-membered heterocyclic and carbocyclic residues, the trends which characterize the stability of these condensed systems are found. The proposed criteria can be used for evaluation of the chemical stability of these compounds, for example, their propensity toward the reverse dissociation reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 532–538, April, 1989.     

Nitroazines. 5. Use of the japp-klingemann reaction for the synthesis of nitrotriazines

Condensation of diazoles with -dicarbonyl nitro compounds (nitromalondialdehyde and nitromalondiester) gives derivatives of azolo[5,1-c] [1,2,4]triazine with a nitro group in the triazine ring.For 4, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 662–665, May, 1986.