Vol 93, No 7 (2023)
Articles
Functionalization of graphene fluoride with 2-phenylbenzimidazole
Abstract
The interaction of graphene fluoride with 2-phenylbenzimidazole afforded a new benzimidazole-functionalized graphene material. It was shown that carrying out the reaction in sulfolane in the presence of pyridine provides a higher degree of functionalization. The formation of the target product was confirmed by elemental analysis, IR and Raman spectroscopy.
Russian Journal of General Chemistry. 2023;93(7):987-994
987-994
Synthesis of N-Substituted Morpholine C60-Fullerene Adducts in the Presence of LiOH and Lead(IV) Acetate
Abstract
A N -phenyl-substituted morpholine adduct of C60 fullerene, 1,9-[4′-phenylmorpholine]-1,9-dihydro-(C60-Ih) [5,6]fullerene, was obtained for the first time with a yield of 56% in the reaction of 2-phenylaminoethanol with fullerene in the presence of LiOH and Pb(OAc)4 at room temperature for 1 h. The amino alcohol with an electron donor group (2-methylaminoethanol) in the reaction with fullerene showed a higher reactivity: the product 1,9-[4′-methylmorpholine]-1,9-dihydro-(С60-Ih)[5,6]fullerene was isolated in 68% yield. The presence of electron-withdrawing groups at the α- or β-carbon atom relative to the nitrogen atom in amino alcohols [carboxylic (2-amino-3-hydroxypropanoic acid, serine) or carbonyl (aminoacetic acid) groups] does not contribute to the reactions with fullerene under the studied conditions.
Russian Journal of General Chemistry. 2023;93(7):995-1000
995-1000
Synthesis of aromatic and heterocyclic fumaropimaric acid triamides
Abstract
A method was developed for the synthesis of previously unknown triamides of fumaropimaric acid by the reaction of anilide and 1-(piperidin-1-ylcarbonyl) derivative of fumaropimaric acid with aromatic and heterocyclic amines [4-toluidine, 4-pentylaniline, 4-biphenylamine, 4-methoxy-, ethoxy-, phenoxy-, bromoaniline, 2-picolylamine, 2-(aminomethyl)furan, 2-(aminomethyl)thiophene] under the action of propanephosphonic acid anhydride.
Russian Journal of General Chemistry. 2023;93(7):1001-1006
1001-1006
Mannich reaction involving 6-amino-4-methyl2-(thio)oxo-1,2-dihydropyridine-3,5-dicarbonitriles
Abstract
The reaction of (1-ethoxyethylidene)malononitrile with cyanoacetamide or cyanothioacetamide yielded 6-amino4-methyl-2-(thio)oxo-1,2-dihydropyridine-3,5-dicarbonitriles. The resulting pyridine derivatives enter into an aminomethylation reaction with an excess of formaldehyde and primary amines with the formation of previously unknown 8-methyl-6-oxo-3-R-1,3,4,6-tetrahydro-2 H -pyrido[1,2- a ][ 1,3,5]triazine-7,9-dicarbonitriles. Further treatment of 6-amino-4-methyl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitrile and its oxygen analogue with excess formaldehyde leads to the formation of 3,10-dimethyl-1,8-dithioxo-5,6,12,13-tetrahydro-1 H ,8 H -dipyrido[1,2- a :1’,2’- e ][1,3,5,7]tetrazocin-2,4,9,11-tetracarbonitrile and 6,6’-[methylenedi(imino)]bis(4-methyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile), respectively. These compounds show a pronounced antidote effect against the herbicide 2,4-D (2,4-dichlorophenoxyacetic acid) in laboratory and field experiments on sunflower seedlings. Also, 6-amino-4-methyl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile exhibits pronounced anticorrosion properties and is an adsorption-type corrosion inhibitor. The mechanism of anti-corrosion action was studied in detail using X-ray photoelectron spectroscopy.
Russian Journal of General Chemistry. 2023;93(7):1007-1022
1007-1022
Pyridine-containing benzocyclopentaquinolines and benzacridines and their quaternary salts
Abstract
Three-component cascade condensation of 2-naphthylamine, pyridinecarbaldehydes, and 1,3-cycloalkanediones in butanol under reflux conditions was used to synthesize 11-pyridinyl-7,8,9,11-tetrahydro-10 H -benzo[ f ]cyclopenta[ b ]quinolin-10-ones and 12-pyridinyl-8,9,11,12-tetrahydrobenzo[ a ]acridin-11(7 H )-ones. Quaternary ammonium salts of a number of benzocyclopentaquinolines and benzoacridines derivatives were obtained.
Russian Journal of General Chemistry. 2023;93(7):1023-1034
1023-1034
Synthesis of 5-[4-(arylsulfanyl)phenyl]-2,2′-bipyridines using aryne intermediates
Abstract
A convenient method for the preparation of 5-aryl-2,2′-bipyridines with para -arylsulfanyl group in an aromatic substituent was proposed. The synthesis was performed using in situ generated aryne intermediates without the use of complex experimental procedures and expensive reagents/catalysts. The structure of one product was confirmed by XRD data. This approach is a new variant for the preparation of 5-aryl-2,2’-bipyridines with an extended conjugation system.
Russian Journal of General Chemistry. 2023;93(7):1035-1042
1035-1042
Synthesis and antimicrobial activity of hexahydrochromeno[4,3-d]pyrimidine-2-thiones thiouronium salts
Abstract
The thiouronium salts of chromeno[4,3- d ]pyrimidine-2-thiones were isolated as individual diastereomers and characterized by 1H, 13C NMR spectroscopy and mass spectrometry. Antibacterial and antifungal activity against sensitive strains of gram-negative bacteria E. coli and P. fluorescens , gram-positive bacteria S. aureus and fungi C. albicans was studied.
Russian Journal of General Chemistry. 2023;93(7):1043-1049
1043-1049
1,3-dipolar cycloaddition of stable azomethine ylide based on ninhydrin and l-proline to phosphorylated acetylenes
Abstract
The reaction of 1,3-dipolar cycloaddition of a stable azomethine ylide formed from ninhydrin and L-proline to activated acetylenic phosphonates was studied. It was found that the reactions proceed under mild conditions with high regioselectivity with the formation of cycloadducts with a spiro[inden-2,3’-pyrrolysine]-1,3-dione backbone.
Russian Journal of General Chemistry. 2023;93(7):1050-1056
1050-1056
New bis-(N,N-diethylamino)(phenethyl)methylsilane and 1,2-bis-(N,N-diethylamino)-1,2-di(phenethyl)1,2-dimethyldisilane
Abstract
New bis-( N , N -diethylamino)(phenethyl)methylsilane and 1,2-bis-( N , N -diethylamino)-1,2-di(phenethyl)-1,2-dimethyldisilane were synthesized by reacting (phenethyl)methyldichlorosilane with diethylamine. Structure of the obtained compounds was confirmed by 1Н, 13С, and 29Si NMR spectroscopy data.
Russian Journal of General Chemistry. 2023;93(7):1057-1060
1057-1060
Synthesis and extraction properties of tripodal tetraphosphoryl ligands on the triphenylphosphine oxide platform
Abstract
New tetraphosphoryl tripodal ligands on the triphenylphosphine oxide platform [2-Ph2P(O)(CH2) n OC6H4]3PO with different linker length ( n = 3, 4) were synthesized. Composition and structure were found by elemental analysis, IR, multinuclear (1H, 13C, 31P) NMR spectroscopy, and X-ray diffraction. Extraction properties of the ligands were studied by the example of recovery of micro amounts of f -block elements from aqueous phase to 1,2-dichloroethane.
Russian Journal of General Chemistry. 2023;93(7):1061-1069
1061-1069
Effect of n-acetylcysteine on cu2+(fe2+)/h2o2-mediated free radical fragmentation of glycerophosphate in the presence of biologically active compounds
Abstract
The effect of N -acetylcysteine on homolytic fragmentation of β-glycerophosphate with cleavage of phosphoester bond was studied. It was shown that, N -acetylcysteine activates the fragmentation induced by Cu2+(Fe2+)-H2O2, and inhibits the radiation-induced process. The stimulated effect of N -acetylcysteine on Cu2+/H2O2-mediated fragmentation in the presence of compounds affecting on HO• level, the Cu2+/Cu+ ratio, or interacting with thiol is either enhanced (Trolox, Ubiquinone Q0) or switched to a prоtective one (NaN3, Met, ascorbate). In the presence of Fe2+ Trolox unlike Q0 reduces the promoter effect of N -acetylcysteine.
Russian Journal of General Chemistry. 2023;93(7):1070-1080
1070-1080
Effect of amino acid fragments in tetraphenylporphin derivatives on the Ph-dominance interval of dication porphyrin
Abstract
The effect of amino acid fragments in tetraphenylporphin derivatives on the pH range of porphyrin dominance as a dication was studied. For this purpose, the protonation processes of unsymmetrically substituted derivatives of 5,10,15,20-tetraphenylporphyrin: 5-(4′-aminophenyl)-10,15,20-triphenylporphine, 5-(4′-tyrosinylamidophenyl)-10,15,20-triphenylporphine and 5-(4′-glycinacylaminophenyl)-10,15,20-triphenylporphine were analyzed in acetonitrile. It was found that in acidic acetonitrile solutions the pH range of dominance of the doubly protonated form depends on the nature of the substituent in the para -position on the periphery of the phenyl fragment of the porphyrin ring: electron-donating substituents expand the pH range of dominance of the porphyrin in the dication form, while electron-withdrawing substituents decrease it. The calculation of the energies of the molecular orbitals of the studied compounds by the DFT method with the B3LYP/cc-pVDZ set showed good agreement between the experimental results and the calculations.
Russian Journal of General Chemistry. 2023;93(7):1081-1087
1081-1087
Application of silver(i) dicyano-[3-cyano-4-(4-dimethylaminophenyl)6-(2-hydroxyphenyl)pyridin-2-yl]methanide as a reagent for the quantitative determination of biothiols
Abstract
An approach for the quantitative fluorimetric determination of a number of anions and thiols, including glutathione and cysteine, based on the use of a silver salt with an organic anion based on nicotinonitrile containing a tricyanobutadiene fragment was proposed.
Russian Journal of General Chemistry. 2023;93(7):1088-1097
1088-1097
Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: XVIII. Synthesis and spectral properties of octasubstituted zinc phthhalocyanines with cyclohexylphenol moieties
Abstract
Using 4-bromo-5-nitro- and 4,5-dichlorophthalonitriles, substituted phthalonitriles containing a fragment of 2-cyclohexylphenol and nitro- or 1-benzotriazolyl groups, as well as phthalonitrile containing two 2-cyclohexylphenoxy groups, were synthesized. Tetramerization of these precursors with zinc acetate hexahydrate gave the corresponding octa-substituted zinc phthalocyanines. Their spectral properties were studied.
Russian Journal of General Chemistry. 2023;93(7):1098-1107
1098-1107
Metal exchange kinetics of asymmetrically substituted cd(II)- tetraarylporphyrins with cobalt and zinc chlorides in dmf
Abstract
The metal exchange reactions of Cd(II)-5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and Cd(II)-5,10,15-tri-(4-nitrophenyl)-20-phenylporphyrin with cobalt and zinc chlorides in dimethylformamide were studied by the spectrophotometric method. The kinetic parameters of metal exchange were calculated and a possible stoichiometric mechanism of the process is established. The influence of the nature of the solvate salt and the chemical modification of the tetrapyrrole macrocycle on the kinetic parameters of the metal exchange reaction was revealed.
Russian Journal of General Chemistry. 2023;93(7):1108-1113
1108-1113
5-(2-pyridyl)tetrabenzoporphyrin and its complexes with zinc, cobalt, copper and iron. synthesis, spectral, electrochemical and electrocatalytic properties
Abstract
The interaction of phthalimide with 2-picoline in the presence of zinc oxide synthesized 3-(pyridin-2-ylmethylene)isoindolin-1-one. Heating its mixture with an excess of phthalimide and zinc acetate leads to the formation of zinc 5-(2-pyridyl)tetrabenzoporphyrinate, which, upon treatment with acid, is converted to 5-(2-pyridyl) tetrabenzoporphyrin. The latter, when interacting with cobalt(II), copper(II), and iron(III) chlorides in DMF, forms the corresponding metal complexes. The composition and structure of the obtained compounds were confirmed by mass spectrometry, vibrational, 1H NMR, and electron spectroscopy. The results of quantum-chemical calculations of complexes by the DFT method are presented. A correlation is established between the energy gap between the frontier orbitals and the positions of the first bands in the electronic absorption spectra. All the synthesized tetrabenzoporphyrins exhibit catalytic activity in the electroreduction of oxygen, the highest activity being exhibited by cobalt and copper complexes.
Russian Journal of General Chemistry. 2023;93(7):1114-1123
1114-1123
Synthesis and physicochemical properties of tin(IV), zirconium(IV), and hafnium(IV) 2(3),9(10),16(17),23(24)-tetrakis-(4-tritylphenoxy)phthhalocyaninates
Abstract
The reaction of 4-tritylphenoxyphthalonitrile with SnCl2, ZrCl4 and HfCl4 in the presence of urea under ammonium molybdate catalysis was used to synthesize tetrakis-(4-tritylphenoxy)phthalocyaninates of tin(IV), zirconium(IV), and hafnium(IV). The complexes were characterized by spectral methods of analysis, including mass spectrometry, 1Н NMR, vibrational and electron spectroscopy. All of them form J -type dimer associates in chloroform at concentrations up to ~1.5×10-6 mol/L and lower, are not associated in a mixture of toluene and pyridine up to concentrations of ~3×10-5 mol/L and higher, have catalytic activity in electroreduction reactions of molecular oxygen. The complexes of zirconium and hafnium showed the highest activity. Tin and zirconium complexes are thermally stable in an inert atmosphere up to a temperature of 200°C.
Russian Journal of General Chemistry. 2023;93(7):1124-1131
1124-1131
Mn(II)-cu(I) hybrid complex based on 1,3,5-tris(diphenylphosphinyl)benzene
Abstract
The reaction of 1,3,5-tris(diphenylphosphinyl)benzene (L) with MnI2 in the presence of CuI (wet MeCN, 25°C, 30 min) leads to the formation of a complex [MnL4(H2O)2][Cu5I7(CH3CN)]·7MeCN with yield of 72%. The Mn2+ ion of this complex has a distorted Mn@O6 octahedral environment formed by four L ligands and two coordinated water molecules. The [Cu5I7(CH3CN)]2- anion has an unprecedented structure of the {Cu5I7} backbone, which includes five copper atoms bound by bridging iodide ions (µ2, µ3, µ4), as well as four short Cu···Cu contacts (<2.80 Å). It is shown that the synthesized complex at 298 K exhibits weak photoluminescence attributed to cluster-centered phosphorescence from the iodocuprate anion.
Russian Journal of General Chemistry. 2023;93(7):1132-1138
1132-1138
Iron-containing polyoxotungstophosphates and their thermolysis products
Abstract
Thermolysis of ferrocenium tungstophosphate [(C5H5)2Fe]3[PW12O40]∙H2O and tungstophosphatoferrates with the general formula of Cat4[PW11O39Fe(H2O)]∙ m H2O, where Cat = (NH4)+, Rb+, Cs+, (CH3)4N+, with the Keggin anion structure were studied using differential scanning calorimetry, infrared spectroscopy, X-ray phase analysis, and electron microscopy. The crystalline products of their thermal decomposition - phases with the structure of pyrochlore and tungsten bronzes - were identified. The synthesized compounds are catalysts for the oxidation reactions of organic compounds and the production of carbon nanomaterials.
Russian Journal of General Chemistry. 2023;93(7):1139-1148
1139-1148