Russian Journal of Organic Chemistry最新文献

The study was aimed at selective synthesis of monoimines from camphor and aliphatic diamines. Among the three diamines used, ethane-1,2-diamine, propane-1,3-diamine, and hexane-1,6-diamine, the latter in an amount of 5 equiv showed the highest selectivity (more than 90%). The selectivity in the reactions with hexane-1,6-diamine and propane-1,3-diamine remained high, whereas in the case of ethane-1,2diamine the selectivity was lower (77.4%). These findings are well explained by the proposed mechanism involving zinc carboxylates as catalysts.

The condensation product of 10-iminophenanthren-9(10H)-one and 3-(furan-2-yl)prop-2-enal in ethanol, 2-[(E)-2-(furan-2-yl)ethenyl]phenanthro[9,10-d][1,3]oxazole, was subjected to electrophilic substitu­tion reactions such as nitration, bromination, sulfonation, formylation, and acylation. Under the given condi­tions, substitution products at the 5-position of the furan ring were obtained.

Acetoacetanilide acetylhydrazone has been synthesized for the first time by the condensation of acetoacetanilide with acetylhydrazide in ethanol. Its structure has been confirmed by elemental analysis, IR and UV spectra, and X-ray analysis. Thermal properties and stability of the title compound have been studied. Acetoacetanilide acetylhydrazone crystallizes in space group P1 of the triclinic crystal system, and its stable crystal packing is determined by a system of intermolecular hydrogen bonds and possible π-stacking interactions. The obtain results suggest that compounds structurally related to acetoacetanilide acetylhydrazone are promising as ligands in coordination chemistry.

A novel electrochemical method for the oxidation of benzyl alcohols to the corresponding ketones is presented. This approach employs a catalytic amount of sodium bromide as a mediator and a source for in-situ generation of bromonium ion, sulfuric acid as a supporting electrolyte, and carbon electrodes in a two-phase medium. Optimization studies revealed that a charge of 2 F yields excellent product conversion at ambient temperature. This methodology demonstrates high selectivity for the oxidation of primary and secondary alcohols to aldehydes and ketones (65–85%), respectively, without forming carboxylic acids. This efficient and environmentally friendly approach offers a promising alternative to traditional oxidation methods.

A new approach has been developed for the synthesis of 2-(5-aryl-2-oxo-1,2-dihydro-3H-pyrrol-3-ylidene)malononitriles by the reaction of 5-arylfuran-2-ones with ammonia, followed by the condensation of the resulting γ-oxobutanamides with tetracyanoethylene.

The reaction of potassium m- and p-aminobenzoates with 3,9-bis(bromomethyl)-2,4,8,10-tetraoxa­spiro[5.5]undecane at a molar ratio of 2:1 gave 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(methylene) bis(3- and 4-aminobenzoates). The latter reacted with 2 equiv of maleic anhydride to produce the corresponding bis-maleamic acids whose intramolecular cyclization in the presence of p-toluenesulfonic acid afforded previously unknown 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(methylene) bis[3- and 4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)benzoates].

Calcium carbide reacted with (4tertbutylphenyl)methanethiol, (4methoxyphenyl)methanethiol, and benzene-1,4dithiol to give the corresponding vinyl sulfides in up to 92% yield. The reaction was successful in the presence of bases, as well as in the presence of potassium fluoride. The synthesized vinyl sulfides can be used to obtain polymers with specified properties.

A preparative method has been developed for the synthesis of previously unknown 3,3,4-trihydroxy­benzimidazo[2,1-b][1,3]thiazinium salts in up to 93% yield by the microwave-assisted reaction of chloro oxiranes and chloro ketones containing an acetal moiety with 1-ethyl-1H-benzimidazole-2-thiol in 95% ethanol. The synthesized compounds are of interest for medicinal chemistry.

A mixture of cobalt(II/III) porphyrazines was synthesized by the reaction of Mg(II) octakis(4-chlorophenyl)tetraazaporphyrin with cobalt(II) chloride in dimethylformamide. Cobalt(III) octakis(4-chloro­phenyl)tetraazaporphyrin was obtained by treatment of cobalt(II/III) porphyrazines in dimethylformamide with 37% hydrochloric acid. The synthesized compounds were identified by UV-Vis, IR, and ¹H NMR spectroscopy and mass spectrometry. The metal exchange reaction of Mg(II) octakis(4-chlorophenyl)tetraazaporphyrin with Co(II) and Cu(II) salts in dimethylformamide was studied by spectrophotometry. The kinetic parameters of the metal exchange reaction were determined, and possible stoichiometric mechanisms were proposed. The influence of the solvate salt nature and chemical modification of the tetrapyrrole macrocycle on the kinetic parameters of the reaction under study was revealed.

The coupled reaction of various dialkyl phosphites with hexamethyldisilazane in the presence of ZnCl₂ at 20°C afforded the corresponding dialkyl trimethylsilyl phosphites in high yields (87–92%). The reaction is complete in 0.5 h, and it requires no specially prepared solvent or inert atmosphere. The initial dialkyl phosphites were synthesized by transesterification of dimethyl phosphite with alcohols in the presence of 0.5 mol % ZnSO₄ at 110–120°C.