卷 59, 编号 4 (2023)
Articles
Synthesis of fluoroalkyl and fluoroaryl substituted hexahydropyrimidines
摘要
The data on the synthesis of fluoroalkyl and fluoroaryl substituted hexahydropyrimidine derivatives from the moment of their first mention are systematized. Predominantly one-pot multicomponent synthesis methods, including catalytic ones, are considered. The effect of the nature of the catalyst, starting reagents, and synthesis conditions on the yield and composition of the resulting products is discussed, and the biological activity of some derivatives is also shown.
Žurnal organičeskoj himii. 2023;59(4):421-436
421-436
Gold-catalysed synthesis of 4-(trifluoromethyl)quinolinecarboxylates
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):437-443
437-443
The synthesis of thioglucoside and their tetracyclic conjugate based on 6-bromo-1,4-naphthoquinone
摘要
A bromine-containing naphthoquinone-carbohydrate conjugate was obtained for the first time by intramolecular condensation of 3-acetylthioglucoside of 6-bromo-2-methoxy-1,4-naphthoquinone under sodium methoxide/ methanol treatment. It has been established that the heterocyclization reaction is accompanied by the substitution of the thioglucoside substituent by the methoxyl group and the formation of an isomeric conjugate.
Žurnal organičeskoj himii. 2023;59(4):444-453
444-453
About acid catalysed acetonation reactions of d-ribose
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):454-465
454-465
Functionalization of 4-hydroxy-6-methyl-2Н-pyran-2-one under the conditions of the modified Biginelli reaction
摘要
The features of the interaction of 4-hydroxy-6-methyl-2 H -pyran-2-one with aromatic aldehydes and urea in the one-pot mode of the classical mode, as well as using thermal and microwave activation of The Biginelli reaction variants, were studied. Depending on the conditions of single-reactory processes, previously unknown 3-[amino(aryl)methyl]-4-hydroxy-6-methyl-2 H -pyran-2-one, arylmethylenebis-4-hydroxy-6-methyl-2 H -pyran2-one, hybrid system - 2-hydroxy-7-methyl-4-(3-nitrophenyl)-4,4a-dihydro-5 H -pyrano[4,3- d ]pyrimidine-5-one in the case of transformation with aryl aldehyde containing an electron-acceptor substitute.
Žurnal organičeskoj himii. 2023;59(4):466-474
466-474
Complex formation of halogen substituted tetraphenylporphyrins and Cd(II)-tetraphenylporphyrins with MnCl2 in DMF
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):475-485
475-485
Synthesis of 2-(3,5-diallyl-2,4,6-trioxo-1,3,5-triazinan-1-yl)ethyl-ureas and -carbamates
摘要
The interaction of 1-(2-aminoethyl)-3,5-diallyl-2,4,6-trioxo-1,3,5-triazinan with phenylisocyanate and 1,6-hexamethylene diisocyanate gave new 3,5-diallyl-and 3,3',5,5'-tetraallylsubstituted isocyanurates containing one and two carbamide groups in their composition. The reaction of 1-(2-hydroxyethyl)-3,5-diallyl-2,4,6-trioxo-1,3,5-triazinan with phenyl isocyanate synthesized 1,3,5-triazinan-1-yl)ethyl-N-phenylcarbamate, and by alkylation of the sodium salt of 3,5-diallyl-2,4,6-trioxo-1,3,5-triazine bis(2-chloroethyl)hexane -1,6-diyldicarbamate was used to prepare bis-[2-(3,5-diallyl-2,4,6-trioxo-1,3,5-triazinan-1-yl)ethyl]hexane-1,6-diyldicarbamate. The physical and spectral properties of the obtained 3,5-di- and 3,3',5,5'-tetraallyl isocyanurates were studied.
Žurnal organičeskoj himii. 2023;59(4):486-491
486-491
Chemical properties of 3-tert-butyl-2-oxo1,2-dihydropyrrolo[1,2-b][1,2,4]triazin-6-carboxylates
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):492-506
492-506
Heterocycles on the base of bis(trifluoromethyl)imidazolidin-2-ones, 2-aminoethanol and 2-aminophenol
摘要
Novel trifluoromethyl-containing imidazo-1,4-oxazines have been synthesized through the condensation reaction of 4,5-dihydroxy-4,5-bis(trifluoromethyl)imidazolidin-2-one with 2-aminoethanol (2-AE) and 2-aminophenol (2-APh). Unusual route of the reaction of 1-methyl(phenyl)- 4,5-dihydroxy-4,5-bis(trifluoromethyl)imidazolidin-2-ones with 2-AE has been found, leading to hydroxyethylamino-substituted hydantoins. The interaction of the N-substituted imidazolidines with 2-APh under similar conditions led to formation of rearrangement products, 5,5-bis(trifluoromethyl)hydantoins. The molecular structure of 5-[(2-hydroxyethyl)amino]-3-methyl-5-(trifluoromethyl)imidazolidin-2,4-dione has been studied by X-ray diffraction experiment.
Žurnal organičeskoj himii. 2023;59(4):507-515
507-515
Decyclization of substituted 3-(4-nitrobenzoyl)hydrasono3H-furan-2-ones under the action of primary alcohols and investigation of analgesic activity and acute toxicity of reaction products
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):516-524
516-524
Heterocyclisation of N-(2-cycloalk-1-en-1-yl-6-methylphenyl)-N-(2-hydroxyethyl)-4-methylbenzenesulfonamides to benzoxazocines
摘要
The article cover the results of a study on the synthesis of benzoxazocines condensed with cycloalkenes. By reacting the corresponding N -tosyl-2-(1-cycloalken-1-yl)anilines with 2-bromoethyl ester of acetic acid, the products of substitution of bromine for the arylamide group were synthesized. The resulting esters were converted by alkaline hydrolysis into N -(2-cycloalk-1-en-1-yl-6-methylphenyl)- N -(2-hydroxyethyl)-4-(methylbenzene)sulfonamides. The interaction of these amides with molecular bromine gives benzo[ e ]cycloalka[ g ][1,4]oxazocine N -tosylates with predominant a R *, R *-stereochemistry, which in solution slowly turn into a S *, R *-atropisomers reaching a ratio of 2.7:1 in the case of cyclohexenyl and 1.4:1 in the case of cyclopentenyl homologues.
Žurnal organičeskoj himii. 2023;59(4):525-534
525-534
Synthesis of 1-antipyryl-1H-pyrrol-2-ones by interaction N-antipyryl substituted enamines with oxalyl chloride
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):535-540
535-540
Synthesis and heterocyclization reaction of tribenzylbenzene sulfonylimino chloride with various polarophiles
摘要
A new method has been developed for the preparation of multifunctional pyrazoles by the reaction of 1,3-dipolar addition of tribenzylsulfonyliminochloride to polarophiles. This imine was obtained by reacting tribenzylamine with N -chlorobenzenesulfamide (chloramine-B). Regardless of the structure and composition of polarophiles, the cyclization reaction takes place in the presence of alkali for 6-8 h of boiling, which proves the activation of the methylene groups of tribenzylamine with the help of an electron-withdrawing sulfamide group.
Žurnal organičeskoj himii. 2023;59(4):541-546
541-546
Synthesis of [(4-methyl-6-oxo-1,6-dihydropyrimidin2-yl)sulfanyl]acetamides
摘要
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.
Žurnal organičeskoj himii. 2023;59(4):547-552
547-552