Volume 88, Nº 10 (2018)
- Ano: 2018
- Artigos: 39
- URL: https://journals.rcsi.science/1070-3632/issue/view/13702
Article
Colloidal and Nanosized Catalysts in Organic Synthesis: XX. Continuous Hydrogenation of Imines and Enamines Catalyzed by Nickel Nanoparticles
Resumo
Nickel nanoparticles on the BAU-A active carbon or NaX zeolite catalyze hydrogenation of imines and enamines in a flow reactor in a gas phase or in a gas–liquid–solid catalyst system. The process occurs at atmospheric pressure of hydrogen and gives secondary or tertiary amines in a high yield.
Unusual Reaction of Sodium 1,6-Dioxo-2,4-alkadiene-3,4-diolates under Acid Hydrolysis Conditions
Resumo
The reaction of sodium 1,6-dioxo-2,4-alkadiene-3,4-diolates with HCl solution afforded unexpected hydrolysis products, namely (2Z)-2-hydroxy-4-oxobut-2-enoic (2,4-dioxobutanoic) acid esters. The structural features of the synthesized compounds were discussed on the basis of IR, 1H NMR spectroscopy, mass spectrometry and X-ray diffraction analysis data.
β-Elimination in 1,1,1-Trichloro-2,2-bis(4-nitrophenyl)ethane by the Action of Sodium Nitrite in Dipolar Aprotic Solvents
Resumo
The kinetics of dehydrochlorination of 1,1,1-trichloro-2,2-bis(4-nitrophenyl)ethane with sodium nitrite in dipolar aprotic solvents have been studied. Quantum chemical simulation of the process has been performed, and its thermodynamic parameters have been determined. The effects of dissociation and solvation on the rate constant have been considered. The reaction mechanism has been identified as E2H.
Some New Reactions and Properties of Xanthane Hydride (5-Amino-1,2,4-dithiazole-3-thione)
Resumo
Aminomethylation of xanthane hydride (5-amino-1,2,4-dithiazole-3-thione) with the RNH2–HCHO system has resulted in the formation of the derivatives of new heterocyclic system (3,7-dihydro-5H-[1,2,4]-dithiazolo[4,3-a][1,3,5]triazine) in low yields. The reaction of xanthane hydride with dicyandiamide has led to thioammeline [4,6-diamino-1,3,5-triazine-2(5Н)-thione]. Some practically important properties of xanthane hydride and its derivatives have been investigated. Xanthane hydride has efficiently exhibited carbon steel corrosion in neutral aqueous media. The prepared compounds have not exhibited growth-regulating or antidote activity to herbicide 2,4-D.
Electrochemical Reduction of Trichlorobiphenyls: Mechanism and Regioselectivity
Resumo
The regioselectivity of electrochemical reduction of four trichlorobiphenyls (PCB 28–30 and PCB 37) was studied by cyclic voltammetry and bulk electrolysis. The number of stages and mechanism of electrochemical reduction of each of the examined substrate were inferred on the basis of the experimental electron transfer coefficients and calculated (DFT) bond lengths and potential energy surface sections. GC/MS analysis of the controlled potential electrolysis products showed that chlorine atom in the disubstituted ring of trichlorobiphenyls is reduced more readily than in the monosubstituted ring and that the rate of chlorine reduction changes in the series o-Cl > p-Cl > m-Cl.
Synthesis of Isomeric Aminomethyl Derivatives of Furylmethanephosphonates
Resumo
By chloromethylation of diethyl 2- and 3-furylmethanephosphonates 5-chloromethylfur-2(3)-ylmethanephosphonates were synthesized. The other four isomers of chloromethyl derivatives of furylmethanephosphonates were prepared by substitution of hydroxy groups in the corresponding phosphorylated furylmethanols via the reaction with thionyl chloride in the presence of pyridine. Thermal stability of these chlorides was sufficiently high, and they were involved in nucleophilic substitution of chlorine with azido group by treating with sodium azide in boiling acetonitrile in the presence of potassium iodide. No decomposition of substrates was observed. The azides obtained were reduced to amines with triphenylphosphine in ethanol.
Reaction of P(IV) Dithio Acids with N-Alkyl-α-chloroketimines
Resumo
Effect of the substituent on the imine carbon atom on the result of the reaction of P(IV) dithio acids with N-Alkyl-α-chloroketimines has been studied. New types of ketones containing (O,O-diisopropyl phosphorothioyl)sulfanyl and (diphenylphosphinothioyl)sulfanyl groups were synthesized.
(Iodomethyl)fluorosilanes: Synthesis and Reactions
Resumo
The methods of synthesis of bifunctional (iodomethyl)fluorosilanes of general formula ICH2SiMenF3–n (n = 0, 2) have been elaborated; the structure was proved by 1H, 13C, 29Si NMR spectroscopy. The reaction of (iodomethyl)dimethylfluorosilane with O-trimethylsilyl derivative of N,N'-dimethylhydrazide of trifluoroacetic acid gives rise to the formation of 2,2,4,4-tetramethyl-6-(trifluoromethyl)-3,4-dihydro-2Н-1,4,5,2-oxadiasilin-4-ium iodide with tetracoordinate silicone atom.
The Reactivity of Ferrocene and Its Derivatives in the Reaction with Quinines
Resumo
The reactivity of ferrocene derivatives with respect to p-quinones in acid media has been studied. A tentative mechanism of oxidation of ferrocene with p-qionone in acid media including two-step reduction of p-quinone to hydroquinone is proposed.
Effect of the Medium on Fluorescence Parameters and Photostability of Porphyrins of Different Structure
Resumo
Fluorescence and photostability against the action of UV irradiation of different porphyrins in benzene, DMF, and acetic acid media have been studied. The effect of the macroheterocycle structure on the conditions of its thermal decomposition under inert atmosphere has been investigated.
Basic and Coordination Properties of Tetraphenylporphine Derivatives
Resumo
Basic and coordination properties of 5,10,15,20-tetrakis(3,5-dibromophenyl)porphine and 5,10,15,20-tetrakis(4-methoxy-3-bromophenyl)porphine in acetonitrile have been investigated by means of spectrophotometry. The optimization of the geometry parameters of polysubstituted porphyrins has been performed using quantum-chemical method (РМ3). The relationship between geometric structure of the studied porphyrins and their coordination, basic, and spectral properties is discussed.
Effect of the Solvent on the Coordination of Pyridine Derivatives with Zn Tetraphenylporphine
Resumo
The coordination of zinc(II) tetraphenylporphine with pyridines was studied by electronic spectroscopy. Linear correlations were found between the thermodynamic and kinetic parameters of coordination in different solvents. The effect of the solvent on the stability constants of the complexes and the thermodynamics of complex formation are discussed.
Coordination Compounds of Cobalt(II), Nickel(II), and Zinc(II) Valerates and Benzoates with Phenylacethydrazide
Resumo
Complexes of cobalt(II), nickel(II), and zinc(II) valerates and benzoates with phenylacethydrazide were synthesized. These compounds were characterized by chemical analysis, IR spectroscopy, diffuse reflection spectroscopy, and thermogravimetry.
Formation of Homo- and Heteronuclear Platinum(II) and Palladium(II) Carbene Complexes in the Reactions of Coordinated Isocyanides with Aminothiazaheterocycles
Resumo
The reaction of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine with cis-dichlorobis(2,6-dimethylphenyl isocyanide)platinum(II) (cis-[PtCl2(CNXyl)2], Xyl = 2,6-Me2C6H3) gave platinum(II) monocarbene complex whose deprotonation with an organic base generated a nucleophilic species capable of reacting with palladium(II) and platinum(II) bis(isocyanide) complexes to afford homo- and heteronuclear isocyanide/carbene structures.
Chemical and Electrochemical Syntheses, Structure, and Luminescent Properties of Zinc and Cadmium Complexes with N-{2-[(E)-(4-tert-Butylphenyl)iminomethyl]phenyl}-4-methylbenzenesulfonamide
Resumo
New Zn(II) and Cd(II) complexes with N-{2-[(E)-(4-tert-butylphenyl)iminomethyl]phenyl}-4-methylbenzenesulfonamide were synthesized by chemical and electrochemical methods. The ligand and metal complexes were characterized by the methods of IR, 1H NMR, electron absorption spectroscopy, and X-ray absorption spectroscopy and by quantum chemical calculations. Electroluminescent devices with zinc and cadmium complexes were fabricated as emitter layers, which showed radiation brightness of 460 cd/m2 (15 V) with a maximum at 502 nm and 140 cd/m2 (15 V) with a maximum at 535 nm, respectively.
Formation of Nd1–xBixFeO3 Nanocrystals under Conditions of Glycine-Nitrate Synthesis
Resumo
Nd1–xBixFeO3 nanocrystals with crystallite size 30‒60 nm have been prepared under conditions of glycine–nitrate burning. Single-phase Nd1–xBixFeO3 nanocrystals are formed over the entire studied concentrations range if the glycine–nitrate synthesis is performed in excess of the oxidizer. Under these conditions, a continuous range of the Nd1–xBixFeO3 solid solutions (0 ≤ х ≤ 0.75) crystallized in the rhombic system (space group Pbnm) are formed without crystallization of the burning intermediates. The Nd1–xBixFeO3 solid solutions (х = 0.775, 0.8) crystallize in the rhombic system (space group Pbаm).
Formation of BiFeO3 Nanoparticles Using Impinging Jets Microreactor
Resumo
The influence of the reactants mixing in an impinging jets microreactor of the formation of singlephase nanocrystals of bismuth orthoferrite has been studied. The 30–100 nm amorphous particles are formed under the impinging jets microreactor conditions, which are converted in bismuth orthoferrite with mean crystallite size 17 nm at 420°С.
Synthesis of Amphiphilic Oligomers of Acrylic Acid
Resumo
Synthesis of amphiphilic oligomers of acrylic acid via radical polymerization in the presence of thiols as molecular mass regulators is described. The effect of the length of the introduced hydrophobic terminal group on the critical micellization concentration of the acrylic acid oligomers has been elucidated. It has been shown that the incorporation of an antituberculous drug (prothionamide) in the micelles of acrylic acid oligomers is enhanced with the increase in the length of the hydrophobic moiety. The preparation of hydroxyapatite-filled calcium-polycarboxylate bone cements containing prothionamide (promising for the sealing of postoperative cavities) is described.
Microwave-Assisted Synthesis and Antimicrobial Activity of 3-(Arylsulfanyl)-4-hydroxy-2H-chromen-2-ones
Resumo
An efficient microwave-assisted synthesis of 3-(arylsulfanyl)-4-hydroxy-2H-chromen-2-ones by condensation of arenesulfonohydrazides with 4-hydroxy-2H-chromen-2-one in the presence of iodine is described. The synthesized compounds were characterized by spectral data (IR, 1H and 13C NMR, and mass spectra and elemental analyses) and were tested for their in vitro antimicrobial activity against bacterial and fungal organisms.
Synthesis, Characterization, Computational, Antimicrobial Screening, and MTT Assay of Thiazolidinone Derivatives Containing the Indole and Pyridine Moieties
Resumo
A series of novel 2-{[1-(arenesulfonyl)-1H-indol-3-yl]-4-oxo-1,3-thiazolidin-3-yl}pyridine-4-carboxamide derivatives was designed and calculate for their computational properties like physicochemical parameters and bioactivity score. Bioactive compounds 1–8, were then synthesized, Characterized by various spercoscopic techniques and assessed for antibacterial activity against S. aureus, S. epidermidis, P. mirabilis, and E. coli. The percent viability of the cells was carried out by MTT assay using HepG2 cells. The results for antibacterial activity were observed in strong recommendation with the computation results. The synthesized compounds were found to portray better activity and lower cytotoxicity when compared to the standard drug Ciprofloxacin.
Metal-Drug Interactions: Synthesis and Spectroscopic Characteristics, Surface Morphology, and Pharmacological Activity of Ephedrine–HCl Complexes with Mo(V), Nb(V), Ga(III), and Ge(IV)
Resumo
Four new Mo(V), Nb(V), Ga(III), and Ge(IV) ephedrine complexes, [Mo(Eph)2(Cl)4].Cl, [Nb(Eph)2(Cl)3], [Ga(Eph)2(Cl)3], and [Ge(Eph)2(Cl)2] are synthesized and characterized. Composition and coordination behavior of ephedrine drug towards Mo(V), Nb(V), Ga(III), and Ge(IV) ions are deduced from microanalysis, IR spectra, molar conductance, magnetic and thermal analysis data. These support coordination of the eph ligand in its neutral state. Ephedrine has two powerful chelating sites, OH and NH, that determine its uni- or bidentate mode of action. IR spectra indicate that Mo(V) and Ga(III) coordinate to ephedrine via nitrogen atom of the NH group as a unidentate chelator with six and five coordination geometry, respectively. On the other hand, Eph ligand behaves as a monoanionic bidentate no chelating agent via the NH and deprotonated OH groups in Nb(V) and Ge(IV) complexes. Mo(V) complex demonstrates electrolytic properties, the other complexes are non-electrolytes in DMSO solutions. TG/DTG analysis makes it possible to calculate the number of solvent molecules in and outside the coordination sphere, and estimate stability of the synthesized complexes. The Eph complexes are screened in vitro for antibacterial (Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis and Staphylococcus aureus) and antifungal (Aspergillus flavus and Candida albicans) activities. Anti-cancer action of the Mo(V) and Ga(III) complexes is assessed against the human hepato cellular carcinoma (HepG-2) tumor cell line (IC50 >1000 μg/mL).
Three New Complexes of Theophylline Drug with Sc(III), Nb(V), and W(VI) Ions: Spectroscopic, Thermal Stability, and Antimicrobial Studies
Resumo
Herein, three newly synthesized theophylline (TPE) complexes with transition metal ions (Sc3+, Nb5+ and W6+) are characterized by FT-IR and UV-Vis spectra, magnetic and thermogravimetric analysis, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmittance electron microscopy (TEM). FT-IR spectra confirm that the metal ions coordinate to TPE chelate as a mono-dentate ligand via nitrogen atom N7 of the deprotonated NH group. Theophylline complexes are formed in 1 : 2 (metal: ligand) stoichiometry. According to TGA curves the complexes do not contain crystallization water outside the binding spheres. The accumulated data indicate the octahedral geometry for Sc(III) and W(VI) complexes. The Nb(V) complex is four coordinated. Sc(III) And W(VI) complexes in DMSO demonstrate non-electrolytic nature, and Nb(V) complex acts as an electrolyte. The TPE complexes are tested in vitro against bacteria (Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis and Staphylococcus aureus) and fungi (Aspergillus flavus and Candida albicans). The complexes exhibit high antimicrobial activity. The in vitro anticancer activity of Sc(III) complex is screened against the human hepato cellular carcinoma (HepG-2) tumor cell line.
Synthesis, Characterization, and Phytotoxic and Antifungal Activities of Biphenyl Derivatives
Resumo
Three series of biphenyl derivatives are synthesized, characterized and evaluated for Lemna minor phytotoxicity and antifungal activity. The synthetic biphenyl analogues 2c and 6c demonstrate significant activity, while compounds 4b and 6b demonstrate high activity. The compounds 2c and 6c can be considered as biaryl-based potential phytotoxic agents. According to in vitro antifungal bioassay the compounds 2b, 2e, and 6b demonstrate moderate activity.
Design, Synthesis, and Anticancer Evaluation of Tetrazole-Fused Benzoxazole Derivatives as Tubulin Binding Agents
Resumo
A novel series of tetrazole fused benzoxazole derivatives 9a–9j are synthesized, and their structures are characterized by 1H and 13C NMR, and mass spectra. The compounds 9a, 9b, 9g, 9h, and 9j demonstrate the highest activity. The compounds 9b and 9g exhibit good anticancer activity, in particular against MCF7, Hop62, and A-549 cell lines with the range of GI50 values from <0.1 to 4.56 μM. Molecular docking study is carried out for the compounds 9a–9j, according to which the compound 9b forms one hydrogen bond with THR766 with the highest docking score (–7.33). This indicates that 9b is effeciently binging to tubulin site.
An Efficient, Eco-Friendly Synthesis of Pyran Annulated Indole Analogs under Conventional Heating and Microwave Irradiation, and Their Anticancer and Antioxidant Activity
Resumo
A rapid, facile, green, eco-friendly, cost effective, and efficient method for the synthesis of pyran annulated indole analogs via one-pot, three components reaction is developed. According to the developed method 2,5-disubstituted-1H-indol-3-carboxaldehyde, malononitrile and various phenols react under MW assisted solvent-free conditions. These compounds can be also prepared under a conventional method that is characterized by some disadvantages in comparison with the above approach. Structures of products are confirmed by FT-IR, 1H and 13C NMR, and mass spectral data. The in vitro antioxidant and cytotoxic activities of the products are evaluated against three tumor cell lines and discussed in terms of structure―activity analysis. Among the screened compounds 3d, 4a, 4b, 5a, and 5b exhibit excellent antioxidant activity. Compounds 4b, 5a, and 5b demonstrate strong cytotoxic activity.
Letters to the Editor
Synthesis of N-Substituted Malonodiimidates
Resumo
The reactions of С-phosphorylated malonodiimidates with acid chlorides in the presence of triethylamine were found to occur selectively under mild conditions and involve acylation of the imino group. The synthesized compounds are most likely to exhibit high antipsoriatic and other biological activities.
Mannich Bases from Bicyclo[2.2.1]hept-5-en-2-ylmethanol, Secondary Amines and Formaldehyde
Resumo
New Mannich bases were synthesized by reacting bicyclo[2.2.1]hept-5-en-2-ylmethanol with secondary amines and formaldehyde. Physicochemical characteristics, composition and structure of the synthesized compounds were determined by elemental analysis, IR, 1H, 13C NMR spectroscopy and mass spectrometry.
Synthesis and Structure of 1-(1,2,3-Thiadiazolylcarbonyl)-4-(1,2,3-thiadiazolyl)semicarbazide Derivatives
Resumo
Novel unknown potentially biologically active 1-(1,2,3-thiadizolylcarbonyl)-4-(1,2,3-thiadiazolyl)-semicarbazides were synthesized by reactions of 1,2,3-thiadiazolylcarboxylic acid hydrazides with 1,2,3- thiadizolylcarbonyl azide in high yields. The structure of the synthesized compounds was studied by NMR and IR spectroscopy and X-ray diffraction analysis.
Synthesis of 5-Phenyl-2,2'-bipyridines 6-Substituted with Donor Groups by aza-Diels–Alder Reactions of 5-R-1,2,4-Triazines under High Pressure Conditions
Resumo
Synthesis of 5-aryl-2,2'-bipyridines with electron-donor substituents at the C6 position by reacting 5-substituted 6-aryl-3-(2-pyridyl)-1,2,4-triazines with 2,5-norbornadiene under high pressure conditions was performed.
Synthesis of Magnetite Nanoparticles in Pores of Mesoporous Silica MSM-41 and Study of Their Magnetic Properties
Resumo
A procedure for the synthesis of superparamagnetic magnetite nanoparticles in pores of mesoporous silica MSM-41 was developed. The dependence of magnetic properties of MSM-41/Fe3O4 nanocomposites on the pore radius of the synthesized silica MSM was studied.
Spectral-Luminescent Properties of 2-(2,6-Difluorophenyl)-5-phenyl-[2-acetyl(benzoyl)oxyphenyl]-1,3,4-oxadiazoles
Resumo
2-(2,6-Difluorophenyl)-5-phenyl(2-hydroxyphenyl)-1,3,4-oxadiazoles were synthesized by cyclization of N-(2,6-difluorobenzoil) derivatives of benzohydazide or salicylhydrazide in thionyl chloride. When acylating 2-[5-(2,6-difluorophenyl)-1,3,4-oxadiazole-2-yl]phenol by acetyl or benzoyl chloride corresponding acetate and benzoate were obtained. Spectral-luminescent properties of the synthesized compounds were studied.
Chemoselective Cross-Coupling of Secondary Phosphine Chalcogenides with Aminophenols: Synthesis of Aminophenylchalcogenophosphinic Acids O-Esters
Resumo
Chemoselective reaction of secondary phosphine chalcogenides with 2-aminophenol under mild conditions (room temperature, 2–4 h, CCl4–Et3N) led to the formation of aminophenylchalcogenophosphinic acids O-esters in a yield of up to 80%.
New Method of Synthesis of Biologically Active Get(aryl)chalcogenylacetates of Tris(2-hydroxyethyl)ammonium
Resumo
Physiologically and pharmacologically active het(aryl)chalcogenylacetates of tris(2-hydroxyethyl)ammonium of pharmacopeial purity have been synthesized by the reaction of het(aryl)chalcogenylacetic acids with sodium (potassium) hydroxide and triethanolamine hydrochloride by one-pot method in quantitative yield (up to 99.8%).
Reaction of 6-Bromo-1,2-naphthoquinone with Tertiary ortho-Anisylphosphines as a Convenient Synthetic Approach to 1,2-Dihydroxynaphthylphosphonium Salts
Resumo
A mild and effective method for the synthesis of new tetraarylphosphonium zwitterions and salts containing methoxy and hydroxy groups in aryl substituents at the phosphorus atom was developed. The structure of phosphorus-containing betaines and phosphonium salts was obtained by NMR spectroscopy.
Preparation of Tin Dioxide Nanoparticles by the Reverse Micelle Method: Experiment and Preliminary Calculations
Resumo
Synthetic and computational experiments were carried out to study the influence of the nature and structure of surfactants, and also of the reaction medium on the size of tin dioxide nanoparticles obtained by the reverse micelle method.
Influence of Modifiers on the Morphology and Functional Properties of Vanadium Dioxide
Resumo
Vanadium dioxide nanoparticles were obtained by the hydrothermal synthesis method in the presence of soluble Mo and W compounds as nucleating agents and of potassium and sodium chlorides as growth limiters. The influence of modifiers nature and synthesis conditions on the phase composition of the resulting product was studied.