Vol 59, No 4 (2023)

An efficient method has been developed for the synthesis of 4-trifluoromethyl-substituted quinolinecarboxylates by the gold(I)-catalyzed reaction of 2’-amino-2,2,2-trifluoroacetophenones with substituted propiolates.

For comparative identification of side products of the cyanation reaction of the imidate donor with trimethylsilyl cyanide, the main compounds formed in the acetonation reactions of D-ribose catalyzed by H₂SO₄, p -TSA, CSA, and PPTS were synthesized and characterized. The structures of the latter were correctly refined by spectral methods using 2D technologies and high-resolution mass spectrometry.

Reactions of complex formation of 5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin, 5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin and metal exchange of their cadmium complexes with manganese chloride(II) in dimethylformamide were investigated. ortho -Substituted manganese complexes were synthesized by prolonged refluxing of the corresponding porphyrins with an excess of MnCl₂ in dimethylformamide. Using the metal exchange reaction of Cd(II)-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin and Cd(II)-5,10,15,20-tetra-(2,6-difluorophenyl) porphyrin, the corresponding Mn(III)-tetraphenylporphyrins were obtained. On the contrary, the coordination reactions of porphyrins substituted at the pyrrole and phenyl rings with manganese chloride in dimethylformamide proceed under mild conditions with the formation of complexes Mn(II)-2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin [the compound oxidizes in air to a mixture of Mn(II) and Mn(III)-porphyrins] and Mn(II)-2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin. The synthesized compounds were identified using UV-Vis, ¹H NMR spectroscopy and mass-spectrometry. Metal exchange reaction of ortho -substituted Cd(II)-porphyrins and complex formation of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin with manganese chloride in dimethylformamide were studied by the spectrophotometric method. The kinetic parameters of the reactions were calculated. A strong effect of β- and ortho -substitution on the reactions of complex formation and metal exchange of the studied compounds was found.

Alkaline hydrolysis of 6- tert -butyl-8-ethyl-7-amino-3- tert -butyl-2-oxo-1,2-dihydropyrrolo[1,2- b ][1,2,4]triazin6,8-dicarboxylate gave the corresponding 8-carboxylic acid, treatment of which with n -BuBr or NBS/TEA led to the decarboxylation and alkylation of N¹, C²O or bromination of the C8 ring position, respectively. Diazotization of 7-amino-3- tert -butyl-8-R¹-2-ОR²-pyrrolo[1,2- b ][1,2,4]triazin-6-carboxylates furnished 7-azido (R¹ = Br, CO₂Et;R¹ = H, n -Bu) and 7-unsubstituted (R¹ = Br, CN; R² = n -Bu, CH₂CO₂Et, CH₂Boc) derivatives, and also 7-(1 H -1,2,3-triazol-1-yl)pyrrolo[1,2- b ][1,2,4]triazin-6,8-dicarboxylate. The spectral and X-Ray structural features, as well as antimicrobial activity of the synthesized compounds are considered.

The decyclization of substituted 3-(4-nitrobenzoyl)hydrazono-3 H -furan-2-ones under the action of primary alcohols, which proceeds with the formation of the corresponding substituted 2-[2-(4-nitrobenzoyl)hydrazono]-4-oxobutanoates, has been studied. The analgesic activity and acute toxicity of the obtained compounds were studied, it was found that the obtained compounds exhibit a pronounced analgesic effect, and also have low toxicity. According to the drug toxicity classification, the obtained primary substituted 2-[2-(4-nitrobenzoyl)hydrazono]-4-oxobutanoates belong to class V of practically non-toxic drugs.

Methyl 4-aryl-2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1 H -pyrazol-4-ylamino)-4-oxo-2-butenoates react with oxalyl chloride to form methyl 3-aroyl-2-chloro-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1 H -pyrazol-4-yl)-4-hydroxy-5-oxo-2, 5-dihydro-1 H -pyrrole-2-carboxylates, which are hydrolyzed to methyl 3-aroyl1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1 H -pyrazol-4-yl)-2,4-dihydroxy-5-oxo-2,5-dihydro-1 H -pyrrole2-carboxylates, the structure of which was confirmed by X-ray diffraction analysis.

The reaction of ethyl-[(4-methyl-6-oxo-1,6-dihydropyrimidin-2-yl)sulfanyl]acetate with aliphatic amines gives corresponding acetamides; the reaction with hydrazine hydrate and aniline leads to 2-hydrazinyl- and 2-anilinopyrimidine respectively.