I. N. Ganebnykh

HETARYL DISPLACEMENT IN 3,6-DISUBSTITUTED 1,2,4,5-TETRAZINES WITH ANHYDRO BASES OF N-METHYLQUINALDINIUMS

3,6-Bis(4-R-3,5-dimethylpyrazol-1 -yl)-s-tetrazine, 3,6-bis(imidazol-1 -yl)-s-tetrazine, 3,6bis(benzotriazol-l-yl)-s-tetrazine,3,6-bis(4-methylimidazol-l-yl)-s-tetrazine react with anhydro bases of 1-methylquinaldium and 1,6-dimethylquinaldium to form products of C-nucleophilic substitution of azolyl fragment or Carboni-Lindsey reaction followed by subsequent pyridine ring cleavage in the quinoline moiety.

Synthesis of 1,3,4,6-tetraoxo compounds

The two-step method of synthesis of 1,3,4,6-tetraoxocompounds with different terminal substituents is developed. By condensation of alkyl methyl ketones with dimethyl oxalate new 1,6-dialkyl-substituted 1,3,4,6-tetraoxohexanes are obtained. The esters of 3,4,6-trioxoalkanoic acids are synthesized by the condensation reaction of alkyl acetates with dialkyl oxalates and alkyl methyl ketones. By the reaction of ethyl acetate with diethyl oxalate and methyl acetate the mixed diester of 3,4-dioxo-1,6-hexanedioic (ketipic) acid has been first prepared. Specific structural features of the synthesized compounds are discussed basing on the data of the IR, NMR, and XRD diffraction (XRD) analysis.

Replacement of dimethylpyrazolyl group in 1,2,4,5-tetrazines by aliphatic alcohols and water

Reactions of 3,6-bis(4-R-3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines and 3-amino-6-(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazines with aliphatic alcohols and water in the presence of a base involved replacement of the dimethylpyrazolyl group and resulted in the formation of mono- and dialkoxy-1,2,4,5-tetrazines and 6-substituted 3-hydroxy-1,2,4,5-tetrazines. Dissociation constants of the latter were determined by potentiometric titration.

Reaction of 1,3,4,6-tetraketones with p-toluidine and benzaldehyde

Reactions of 1,6-diphenylhexane-1,3,4,6-tetraone, octane-2,4,5,7-tetra-one, and decane-3,5,6,8-tetraone with a mixture of p-toluidine and benzaldehyde afforded, respectively, 2-[4-benzoyl-3-hydroxy-1-(4-methylphenyl)-5-phenyl-1H-pyrrol-2-yl]-1-phenylethanone, (1E)-1-[4-acetyl-3-hydroxy-1-(4-methylphenyl)-5-phenyl-1,5-dihydro-2H-pyrrol-2-ylidene]propan-2-one, and 2-hydroxy-1-(4-methylphenyl)-2-(2-oxobutyl)-4-propanoyl-5-phenyl-1,2-dihydro-3H-pyrrol-3-one.

Synthesis and Tuberculostatic Activity of Some Substituted Amino Acid Methyl Esters with Sym-Tetrazine Moieties

The products of nucleophilic substitution of methyl esters of seven amino acids for the 3,5-dimethylpyrazolyl moiety in 3,6-bis(3,5-dimethylpyrazol-l-yl)-5-tetrazine were obtained. One of these compounds exhibited tuberculocidal action at a concentration of 0.6 μg/ml. In contrast, two other compounds stimulated the growth of mycobacterium colonies.

Synthesis of oxocyclohexenecarboxylic acids and podands derived therefrom under heterogeneous catalysis

Nanosized Al, Mg, and Ti-Si oxides, as well as barium hydroxide, have been tested as heterogeneous catalysts in the Robinson reaction with 2-ethoxy-substituted chalcone and podands based thereon. Barium hydroxide catalyzes the first step of the Robinson reaction, Michael addition, while its activity in the second step involving intramolecular cyclization and dehydration is lower. Nanosized oxides effectively catalyze the second step of the Robinson reaction and hamper elimination of the carboxy group. Procedures have been developed for the synthesis of oxocyclohexenecarboxylic acid derivatives and symmetric and asymmetric podands based thereon.

Reactions of 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5-tetrazines with indole and 1,3,3-trimethyl-2-methyleneindoline

It has been found that 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5- tetrazines react with indole and 1,3,3-trimethyl-2-methyleneindoline to give pyridazines as (4+2)cycloaddition products. 1,3,3-Trimethyl-2-methyleneindoline has been shown to act as C-nucleophile in the substitution of pyrazolyl group as well as in the reactions of tetrazine ring expansion in

Reaction of 3,4,6-trioxoalkanoic acid esters with 2,4-dinitrophenylhydrazine

Methyl 3,4,6-trioxoalkanoates (3,4-dihydroxy-6-oxo-2,4-alkadienoates) reacted with 2,4-dinitrophenylhydrazine to give methyl 3,6-bis[(2,4-dinitrophenyl)hydrazinylidene]-4-oxoalkanoates or methyl {5-alkyl-2-hydroxy-1-(2,4-dinitroanilino)-3-oxo-2,3-dihydro-1H-pyrrol-2-yl }acetates. Alkyl 3,6-bis[(2,4-dinitrophenyl) hydrazinylidene]-4-oxoalkanoates were also synthesized by reaction of disodium 1-alkoxy-1,6-dioxoalka-2,4-diene-3,4-diolates with 2,4-dinitrophenylhydrazine.

Synthesis and structural peculiarities of disodium 1,6-dioxoalka-2,4-diene-3,4-diolates

Three-component condensation of dialkyl oxalates with alkyl acetates and alkyl methyl ketones in the presence of bases afforded 1-alkoxy(or 1,6-dialkoxy)-1,6-dioxoalka-2,4-diene-3,4-diolates. The product structure was discussed on the basis of their IR, 1H NMR, and mass spectra.

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.