Том 93, № 1 (2023)
Articles
Selective synthesis of some carboxylic acids esters
Аннотация
The synthesis of esters of some carboxylic acids by the method of oxidative esterification was carried out. It was shown that the proposed method allows the selective esterification of carboxylic acids with hindered carboxyl groups. It was found that the synthesized esters have anti-aggregation activity at the level of acetylsalicylic acid.
Russian Journal of General Chemistry. 2023;93(1):3-10
3-10
2E,2′E)-2,2′-(1,2,4-Thiadiazole-3,5-diyl)bis[3-arylacrylonitriles]: Synthesis and Antidote Activity with Respect to 2,4-D Herbicide
Аннотация
Oxidation of ( Е )-3-aryl-2-cyanothioacrylamides under the action of the Et2S(O)-HCl system leads to the formation of (2 Е ,2' E )-2,2'-(1,2,4-thiadiazole-3,5-diyl)bis[3-arylacrylonitriles] in 54-91% yields. Structure of the obtained compounds was confirmed by the two-dimensional NMR spectroscopy data. A plausible reaction mechanism was discussed. Two compounds showed a pronounced antidote effect against 2,4-D herbicide in a laboratory experiment on sunflower seedlings in the absence of growth-stimulating activity.
Russian Journal of General Chemistry. 2023;93(1):11-21
11-21
Synthesis and antibacterial activity of 4-oxo-2-thienylaminobut-2-enoic acids
Аннотация
The hydrolysis of substituted 3-(3-cyanothiophen-2-yl)imino-3 H -furan-2-ones was studied. It was found that the reaction proceeds with the opening of the furan ring and the formation of the corresponding 4-oxo-2-(3-cyanothiophen-2-yl)aminobut-2-enoic acids. The antibacterial activity of the obtained compounds against Staph ylococcus aureus , Escherichia coli and Candida albicans was studied.
Russian Journal of General Chemistry. 2023;93(1):22-30
22-30
Synthesis and some properties of 2-amino-4-aryl-6-hexyl7-hydroxy-4h-chromene-3-carbonitriles
Аннотация
Three-component condensation of aromatic aldehydes with malononitrile and 4-hexylresorcinol in toluene in the presence of a base leads to the formation of 2-amino-4-aryl-6-hexyl-7-hydroxy-4 H -chromene-3-carbonitriles in good yields (79-90%). Structure of the compounds was studied using the methods of two-dimensional NMR spectroscopy. Bioavailability parameters were predicted in silico , and possible protein targets were predicted by protein-ligand docking.
Russian Journal of General Chemistry. 2023;93(1):31-42
31-42
Biginelli reaction in the synthesis of ethyl 4-(6-aryl-5-benzoyl-4-hydroxy-2-thioxohexahydropyrimidine-4-carboxamido)benzoates
Аннотация
Three-component Biginelli reaction of ethyl 4-(2,4-dioxo-4-phenylbutanamido)benzoate, aromatic aldehyde and thiourea in acetic acid in the presence of sodium acetate led to the formation of ethyl 4-(6-aryl-5-benzoyl4-hydroxy-2-thioxohexahydropyrimidine-4-carboxamido)benzoates. Structure of the obtained compounds was established by IR, 1H NMR, 13C spectroscopy methods.
Russian Journal of General Chemistry. 2023;93(1):43-49
43-49
Reaction of c-alkyl-substituted 1,4,8,11-tetraazacyclotetradeca-4,11-dienes with carboxylic acid halides as a new method for the synthesis of c- and N-acyl-2,3,6,7-tetrahydro-1,4-diazepines
Аннотация
The reactions of 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene with acetic and tetrafluorobenzoic acids halides produce C - and N -acyl-substituted 1,4-diazepines. Their structure was characterized by IR, 1H, and 13C NMR spectroscopy using two-dimensional experiments 1H-13C HMQC, HMBC, and 1H-1H COSY.
Russian Journal of General Chemistry. 2023;93(1):50-57
50-57
Synthesis, structure and non-covalent interactions of 5-methyl-2,3-dihydrothiazolo[2,3-b]thiazolium halides
Аннотация
2,3-Dihydrothiazolo[2,3- b ]thiazolium iodides and bromide were obtained for the first time by the cyclization of corresponding metallyl- and propinylsulfanyl derivatives of 1,3-thiazole with iodine and bromine in dichloromethane without heating and the use of strong acids. The structure of the obtained compounds was studied by 1H, 13C{1H} NMR spectroscopy. Structure of the 3-iodomethyl-3,5-dimethyl-2,3-dihydrothiazolo[2,3- b ][1,3]thiazolium heterocyclic system is characterized by the X-ray analysis. The bonding in the heterocyclic system and non-covalent cation-anion interactions are analyzed on the basis of quantum chemical calculations with periodic boundary conditions; I···S chalcogen bond is discussed.
Russian Journal of General Chemistry. 2023;93(1):58-66
58-66
Synthesis and structure of 4-aryl-3,6-dioxo-2,3,4,5,6,7-hexahydroisothiazolo[5,4-b]pyridine-5-carbonitriles
Аннотация
Oxidation of triethylammonium 6-amino-4-aryl-3-carbamoyl-5-cyano-1,4-dihydropyridine-2-thiolates with DMSO-HCl system leads to the formation of novel 4-aryl-3,6-dioxo-2,3,4,5,6,7-hexahydroisothiazolo[5,4- b ]pyridine-5-carbonitiriles. Structure of the obtained compounds was studied using two-dimensional NMR spectroscopy and HRMS methods. An in silico predictive analysis was carried out to identify bioavailability parameters and possible protein targets for the obtained compounds.
Russian Journal of General Chemistry. 2023;93(1):67-76
67-76
Photochemical production of molecular hydrogen in the presence of substituted acridine salts
Аннотация
The photocatalytic properties of new representatives of the family of metal-free catalysts, 10-hydro-9-phenylacridine, 10-methyl-9-phenylacridinium chloride, and 10-phenyl-9-phenylacridinium chloride, were studied with respect to the reaction of molecular hydrogen generation in the presence of acids of different strength (HClO4, CH3SO3H, and CF3COOH) and reducing agents ([Bu4N]Cl, [Bu4N]Br, and [Bu4N]I). It was found that the strength of acids (p K a) and the nature of the reducing agent ( E 0) significantly affect the efficiency, i.e. turnover frequency (TOF), of the process under study. The amount of formed molecular hydrogen reaches its maximum in the case of the combination HClO4 and [Bu4N]I, characterized by minimal p K a and E0 values, respectively. The influence of the nature of substituents at the nitrogen atom in 9-phenylacridine on the efficiency of the molecular hydrogen production was analyzed. It was shown that the limiting stage of the process is the protonation of the formed radical.
Russian Journal of General Chemistry. 2023;93(1):77-83
77-83
Synthesis of bis-α-hydroxyphosphine oxides based on salicyl aldehyde scaffold
Аннотация
By addition of secondary phosphine oxides to dicarbonyl compounds obtained by binding two salicylaldehyde molecules with ether-type spacers, previously unknown bis-α-hydroxyphosphine oxides were synthesized. The obtained compounds are of interest as potential biologically active substances, complexing agents and initial building blocks in the synthesis of macrocyclic compounds bearing pendant phosphorus-containing substituents.
Russian Journal of General Chemistry. 2023;93(1):84-90
84-90
Synthesis, structure, and properties of 2-oxo-3-formylquinolone acylhydrazone containing a trimethylammonium fragment and also of transition metal complexes based on this compound
Аннотация
The product of 3-formyl-2-quinolone condensation with trimethylammonium chloride acethydrazide, (H2L+)Сl- hydrazone, was synthesized. Complexes of Zn(II) and Cu(II), [M(HL)OCH3]ClO4, with a distorted square-planar strucrure of coordination sites and asymmetric chelate сomplexes of Mn(II), Ni(II), and Co(II), [M(HL) (H2L)]·(ClO4)3, of pseudo-octahedral structure were obtained on its basis. The protistocidal, antibacterial, and fungistatic activities of the synthesized compounds were studied.
Russian Journal of General Chemistry. 2023;93(1):91-105
91-105
Synthesis of 2-heteroylidene triterpenoids: complex formation with palladium and cytotoxic activity in vitro
Аннотация
Triterpenoids with a pyridinylmethylidene substituent in the C2 position were prepared via the reaction of betulonic acid with pyridine-2-carbaldehyde, pyridine-3-carbaldehyde, pyridine-4-carbaldehyde or quinoline-2-carbaldehyde. The products were tested as ligands for palladium(II). Two ligands and one complex were prepared for the first time. The structures of new compounds were confirmed by 1D and 2D NMR spectra, as well as by electrospray ionization mass spectra. The E -isomerism of pyridinylmethylidene substituent in the C2 position of triterpenoid was proved. Cytotoxic activity of the complexes with respect to A549 (adenocarcinomic human alveolar basal epithelial cells) cell line was estimated.
Russian Journal of General Chemistry. 2023;93(1):106-112
106-112
Bisisocyanide cyclometallated platinum(II) complexes: synthesis, structure, photophysical properties, and mechanochromic behavior
Аннотация
A series of cyclometallated platinum(II) complexes [Pt(ppy){CNAr}2]X with two isocyanide ligands (Hppy = 2-phenylpyridine, Ar = C6H2-2,4,6-Me3, C6H3-2-Cl-6-Me , C6H3-2,6-Cl2, C6H4-4-NMe2, C6H4-4-Me, C6H4 4-Cl, C6H4-4-Br, C6H4-4-I, C6H4-4-CF3, C6H4-3-CF3; X = BF4, OTf) was synthesized by the reaction of the [{Pt(ppy)Cl}2] dimer with isocyanides (yield 52-70%). The structure of the resulting complexes was determined using mass spectrometry, 1H, 13C{1H}, 195Pt{1H}, 1H-1H COSY, 1H-1H NOESY, 1H-13C HSQC, and 1H-13C HMBC NMR spectroscopy in solution and solid-state CP/MAS 13C and 195Pt NMR spectroscopy, IR spectroscopy and X-ray diffraction analysis in the solid phase. The photophysical properties of the obtained complexes in the solid phase and the mechanochromic luminescence behavior were studied. In the solid phase, all synthesized compounds phosphoresce in the green or orange range of visible light, while photoluminescence quantum yields reach 26%. Green phosphors exhibit a reversible mechanochromic luminescence change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).
Russian Journal of General Chemistry. 2023;93(1):113-125
113-125
Structure and stability of nickel(II) complexes with cryptand[2.2.2]
Аннотация
The values of the stability constants of the mononuclear, protonated and binuclear complexes of nickel(II) with cryptand [2.2.2] were determined using potentiometric titration at ionic strength value µ→0 and temperature of 298 K. The structure and the most important geometric characteristics of Ni2 + cryptates were optimized via quantum chemical calculations performed in vacuo .
Russian Journal of General Chemistry. 2023;93(1):126-134
126-134
Magnetic susceptibility La1-0.397xGd0.067xCa0.33xMnхAl1-хO3 solid solutions
Аннотация
Solid solutions of lanthanum manganites with perovskite structure containing calcium and gadolinium atoms were studied by the method of magnetic dilution. The obtained magnetic characteristics and the character of their temperature changes point to a clustering of magnetic atoms in the perovskite structure. A comparison of the solid solutions under study with La1- y Gd y AlO3 testifies for gadolinium atoms taking part in the exchange interactions in the La1-0.397 х Gd0.067 х Ca0.33 х Mn х Al1- х O3 solid solutions.
Russian Journal of General Chemistry. 2023;93(1):135-138
135-138
State of manganese atoms in La1-0.55xEu0.13xSr0.35xMnxAl1-xO3 solid solutions
Аннотация
Solid solutions of lanthanum manganites in LaAlO3 doped with europium and strontium atoms are studied by the method of magnetic dilution. The magnetic clusters were found including manganese and europium atoms with ferromagnetic type of exchange interactions.
Russian Journal of General Chemistry. 2023;93(1):139-145
139-145
High-temperature synthesis of cobalt nanoparticles in hyperbranched polyester polyol medium
Аннотация
The synthesis of CoNPs cobalt nanoparticles by the method of polyol- process was proposed, which consists in a high-temperature synthesis of polymer-stabilized metal nanoparticles in a matrix of a fourth-generation hyperbranched polyester polyol. Branched polyester polyol acts as both a reducing agent and a stabilizer at the same time. It has been found that the reduction of the precursor CoCl2 with a hyperbranched polyester polyol occurs at 210°C. The introduction of NaOH into the reaction mixture makes it possible to lower the synthesis temperature by 50°C and leads to a change in the mechanism of in situ ripening CoNPs from the digestive mechanism to direct Ostwald ripening.
Russian Journal of General Chemistry. 2023;93(1):146-152
146-152
Effect of alkaline activation on the structural characteristics of nanocomposites based on carbonized chitosan and Fe-Co bimetallic nanoparticles
Аннотация
Metal-carbon nanocomposites consisting of Fe-Co bimetallic nanoparticles uniformly dispersed in the carbon matrix were synthesized by pyrolysis of a precursor based on chitosan and metal salts in the temperature range 500-800°C. The change in the structural characteristics of the samples after activation in the presence of potassium hydroxide was studied. It was found that alkaline activation leads to an increase in the specific surface area of the nanocomposites up to 700 m2/g and in the size of metal nanoparticles, whereas the phase composition and morphology of the carbon support remain unchanged.
Russian Journal of General Chemistry. 2023;93(1):153-164
153-164