Vol 89, No 10 (2019)
- Year: 2019
- Articles: 30
- URL: https://journals.rcsi.science/1070-3632/issue/view/13715
Article
Colloid and Nanosized Catalysts in Organic Synthesis: XXII. Hydrogenation of Cycloolefins Catalyzed by Immobilized Transition Metals Nanoparticles in a Three-Phase System
Abstract
The processes of unsaturated cyclic hydrocarbons hydrogenation in a three-phase gas-liquid-solid catalyst system in the presence of nanostructured nickel, cobalt, or iron catalysts in a flow reactor at 130°C and atmospheric pressure have studied. RX3Extra activated carbon, γ-Al2O3, NaX zeolite, and Purolite CT-175 cation-exchange resin have been used as supports; NaBH4 and NH2NH2·H2O were used as reducing agents. The catalytic activity of supported nanoparticles and their selectivity with respect to the product of exhaustive hydrogenation have been investigated.
Reactivity of Selected Mono- and Dimethylpyridines under Conditions of Oxidative Ammonolysis
Abstract
The reactivity of 3-methyl-, 4-methyl-, 2,3-dimethyl-, and 3,4-dimethylpyridines under the oxidative ammonolysis on vanadium oxide catalysts has been studied. The yield of monocyanopyridines has been related to the simulated values of the deprotonation enthalpy of methyl substituents being converted into the cyano group, both in the gas phase and under conditions simulating chemisorption at the acid center of the catalyst. Differences in the mechanism of conversion of the primary products of oxidative ammonolysis of 2,3- and 3,4-dimethylpyridines (2-cyano-3-methyl- and 4-cyano-3-methylpyridines) at elevated temperature have been revealed.
Synthesis of Tetradecapentaenoic Acid Derivatives
Abstract
A 12-stage method for the stereoselective synthesis of tetradecapentaenoic acid derivatives using phosphoric reagents was developed. The key step in the synthesis is the Z-selective Wittig reaction between sorbaldehyde and triphenylphosphonium (6-methoxycarbonyl)hexanilide, as well as the Ramirez-Corey-Fuchs reaction and the Trost-Kazmaier rearrangement. The synthesized (2E,4E,8Z,10E,12E)-N-isobutyltetradeca-2,4,8,10,12-pentaenamide corresponds to a natural compound called γ-Sanshoöl.
Reaction of 2-[Aryl(alkyl)amino]malonates with Chloroethynylphosphonates
Abstract
Preparative limitations of the reaction of chloroethynylphosphonates with 2-(alkylamino)malonates have been established. Unlike the reaction of chloroethynylphosphonates with 2-(arylamino)malonates which involve only the carbon nucleophilic center, 2-(alkylamino)malonates react through both carbon and nitrogen atoms. The geometric structural, energetic, and charge parameters of the optimized structures of aliphatic and aromatic diethyl 2-aminomalonates have been determined by quantum chemical calculations using Gaussian 03 software, and pKa values for both nucleophilic centers in their molecules have been calculated.
Synthesis and Biological Activity of New 2-{[6-Methyl-2-(pyrrolidin-1-yl)pyrimidin-4-yl]oxy}acetohydrazide Derivatives
Abstract
The reaction of 6-methyl-2-(pyrrolidin-1-yl)pyrimidin-4(3H)-one with methyl chloroacetate, followed by hydrazinolysis, gave 2-{[6-methyl-2-(pyrrolidin-1-yl)pyrimidin-4-yl]oxy}acetohydrazide, and the latter was used to obtain a series of new derivatives, including those containing a 1,2,4-triazole, 1,3,4-oxadiazole, or furan ring in addition to the pyrimidine fragment. Preliminary biological screening of the synthesized compounds revealed a pronounced plant growth stimulating effect at a level of 65–87% relative to heteroauxin.
Synthesis and Cyclizations of N-(Thieno[2,3-b]pyridin-3-yl)cyanoacetamides
Abstract
3-Aminothieno[2,3-b]pyridine-2-carboxylic acid esters readily reacted with 3,5-dimethyl-1-(cyanoacetyl)-1H-pyrazole to give previously unknown N-(thieno[2,3-b]pyridin-3-yl)cyanoacetamides. Reactions of the latter with 2-(arylmethylidene)malononitriles were nonselective, and mixtures of different heterocyclization products were generally formed. The cyclization of ethyl 4,6-dimethyl-3-[(cyanoacetyl)amino]thieno[2,3-b]-pyridine-2-carboxylate afforded 2,4-dihydroxy-7,9-dimethylthieno[2,3-b : 4,5-b′]dipyridine-3-carbonitrile whose tautomeric equilibrium was studied by DFT quantum chemical calculations. In silico analysis of biological activity of the synthesized compounds was performed.
Synthesis of 2-Substituted 5-(1,2,3-Selenadiazol-4-yl)furan-3-carboxylic Acids Esters
Abstract
A series of semicarbazones have been obtained from 2-substituted 5-acetylfurancarboxylic acid esters. When oxidized with selenium dioxide in acetic acid, 5-(1,2,3-selenadiadiazol-4-yl)furan-3-carboxylic acid esters bearing a functional group in position 2 of the furan ring have been formed.
Some Features of Phosphorylation of 4-Substituted Thiosemicarbazides with Chloroethynylphosphonates
Abstract
The reactions of chloroethynylphosphonates with 4-substituted thiosemicarbazides leads to the predominant formation of dialkyl esters of 5-substituted (1,3,4-thiadiazol-2-yl)methylphosphonic acids with an admixture (up to 31%) of dialkyl [3-amino-2-(alkylimino)-2,3-dihydro-1,3-thiazol-4-yl)phosphonates as a minor product.
Synthesis, Structure, and Biological Activity of Cinnamoyl-Containing Cytisine and Anabasine Alkaloids Derivatives
Abstract
The reactions of the cytisine and anabasine alkaloids with cinnamic acid chloride have been studied, and hydrazinolysis of the resulting N-cinnamoylcytisine and N-cinnamoylanabazine has been carried out. The reaction of cinnamoyl isothiocyanate with alkaloids has afforded the corresponding thiourea derivatives. Antimicrobial and cytotoxic activity of cinnamoyl-containing derivatives of these alkaloids has been evaluated.
Complexation of 2,3-Dimethyl-5-hydroxy-6-aminopyrimidin-4(3H)-one with Copper(II) Ions in Nonaqueous Solutions
Abstract
Complex formation of 2,3-dimethyl-5-hydroxy-6-aminopyrimidine-4(3H)-one with copper(II) ions in nonaqueous solutions has been studied by means of electron, NMR, and IR spectroscopy as well as mass spectrometry. Sequential formation of tetra- and pentacoordinated copper(II) complexes with mono- and bidentate ligand coordination has been observed. The complexes composition has been determined by spectrophotometry using the molar ratios method. Donor centers of the ligand involved in coordination with copper(II) ions have been determined, and the complexes formation constant have been calculated.
Synthesis and Spectral-Luminescent Properties of Octa-substituted Aluminum Phthalocyanines Bearing Biphenyloxy Groups
Abstract
Mixed-substituted aluminum phthalocyanines bearing biphenyloxy substituents and nitro groups or 1-benzotriazole moieties in the periphery were synthesized on the basis of the previously obtained 4,5-disubstituted phthalonitriles. The spectral-luminescent properties of the resultant compounds were studied.
Synthesis and Properties of C,N-Chelated Carbene Complexes of Palladium(II) with 2-Aminobenzo[d]thiazole Fragment
Abstract
The reaction of bis(cyclohexylisocyanide) complex of Pd(II) with substituted benzo[d]thiazole-2-amines in the presence of triethanolamine as the base has lead to the formation of deprotonated C,N-chelated carbene complexes with a structure similar to that described previously for the products of the reaction with unsubstituted benzo[d]thiazole-2-amine. The complexes have been isolated and characterized using high-resolution mass spectrometry, IR and NMR spectroscopy (1H, 13C{1H}, 1H-1H COSY, 1H-1H NOESY, 1H-13C HSQC, 1H-13C HMBC). The resulting complexes have exhibited moderate antibacterial activity against sensitive strains of gram-negative bacteria E. coli (C600) and P. fluorescens (P218), gram-positive bacteria S. aureus (ATCC-25923) and B. subtillis (B-3142D) as well as fungi C. albicans (401/NCTC-885-653).
Boron Carbide Secrets
Abstract
The issues of the composition-structure relationship of boron carbide are discussed. A new hypothesis based on the presence of channels with a diameter of 2.7–2.9 Å in crystals, into which C or B atoms can be intruded, has been proposed. The intrusion has been confirmed by the data of quantum-chemical simulation using VASP program. It has been shown that the introduction of atoms into the channels changes the cell parameters and deforms the structural fragments. The latter may cause the formation of monoclinic crystals of boron carbide. According to the quantum chemical simulattions, the cell parameters of boron carbide crystals of the same composition depend on the site of intrusion of the C atoms into the channels.
Synthesis of Nanocrystalline Materials Based on the Bi2O3-TiO2 System
Abstract
Nanocrystalline bismuth titanates Bi2Ti4O11 (115±5 nm), Bi4Ti3O12 (60±5 nm), Bi2Ti2O7 (105±5 nm), Bi8TiO14 (82±5 nm), and Bi12TiO20 (102±5 nm) were synthesized by heat treatment of the coprecipitated composition. It was revealed that the crystallite sizes of the target materials are determined by the minimum crystallite size of the first phase to crystallize in the reaction system. The process parameters of the synthesis and of the sintering of the materials were found to depend on the melting point of the surface (nonautonomous) phase. It was shown that the formation of the materials is mainly influenced by the kinetic factor, and the influence of the structural features is less pronounced.
Effect of Star-Shaped Modifiers on the Transport Properties of Polymer Composites in the Butan-1-ol Dehydration Process
Abstract
New polymer composites were obtained by incorporating hybrid carbon modifiers into the poly(m-phenyleneisophthalamide) matrix consisting of a branch center (C60 fullerene) and 12 grafted hydrophobic chains: 6 polystyrene chains and 6 poly(tert-butyl methacrylate) chains. The physico-chemical and transport properties of the membranes were studied for the purification of butan-1-ol from water impurities.
Structure and Properties of Nanocomposites Prepared via the Environmental Crazing of Poly(ethylene terephthalate) in Solutions of Polyelectrolyte Complexes
Abstract
Deformation of amorphous poly(ethylene terephthalate) (PET) in solutions of polyelectrolyte complexes (PEC) of poly(ethylene glycol) with alkali metal salts (potassium thiocyanate or sodium perchlorate) has occurred via the crazing mechanism and has resulted in the formation of a porous structure being filled with PEC during the drawing. The content of PEC in the nanocomposite has increased with the increase in the draw ratio (up to 55%). The hybrid nanocomposites obtained via the crazing have exhibited anisotropy of surface electroconductivity which has been determined by the structural features of the deformed polymer matrix.
Interaction of Glutathione-Stabilized Gold Nanoclusters with Doxorubicin and Polycation
Abstract
Glutathione-capped gold nanoclusters display polyanionic properties that are manifested in the interaction with cationic species. The nanoclusters form complexes with doxorubicin with effective dissociation constant about 10 µM that increased by an order of magnitude in the presence of 0.15 M NaCl confirming electrostatic character of binding. Adsorption of polylysine arose an increase in the fluorescence of gold nanoclusters due to aggregation induced emission enhancement effect. Fluorescence of the complexes increased several-fold upon addition of up to 1 M of KCl suggesting contribution of non-Coulombic forces in the stabilization of aggregates of gold nanoclusters.
Synthesis of the Tripeptides Tyr-Thr-Lys Phosphorylated with Isopropyl Methyl- and (Deuteromethyl)phosphonochloridates as Reference Standards for the Analysis of Biomedical Samples
Abstract
A procedure for the phosphorylation of the tripeptide Tyr-Thr-Lys with isopropyl methyl- or (deuteromethyl)phosphonochloridate is developed. The phosphorylated tripeptides are intended for use as reference standards in the analysis of blood samples of people suspected to have been exposed to acetylcholinesterase inhibitors. Conditions of hromatographic separation and purification of the synthesized compounds are determined and optimized, which ensures the preparation of high-purity phosphorylated tripeptides.
Design, Synthesis, Antimicrobial, and Antioxidant Activity of Dimers of Chromene Containing 1,2,3-Triazole Derivatives Bearing an Alkyl Spacer
Abstract
A new series of chromene based 1,2,3-triazole derivatives has been synthesized by incorporating biologically active heterocyclic rings containing chromene and triazole moieties in one molecular structure. All newly synthesized compounds are characterized by 1H and 13C NMR, mass, and IR spectra. The title compounds are tested for their activity against different bacterial and fungal strains, and antioxidant activity. Several compounds are determined to be potent antimicrobial and antioxidant agents.
Design, Synthesis, and Evaluation of Isoxazole-Thiadiazole Linked Carbazole Hybrids as Anticancer Agents
Abstract
A series of isoxazole-thiadiazole linked carbazole derivatives 12a–12j are synthesized and their chemical structures confirmed by 1H and 13C NMR and mass spectra. The products are tested for their anticancer activity against human cancer cell lines: MCF-7 (breast), A549 (lung), DU-145 (prostate), and MDA MB-231 (breast) by using MTT assay and etoposide as a reference drug. The accumulated data indicate that most of the compounds demonstrate anticancer activity higher than etoposide.
Synthesis, Characterization, and Anti-Diabetic Therapeutic Activity of New Vanadyl(II) Complexes with Orotic Acid and Different Amino Acids Mixed Ligands
Abstract
Mixed ligand vanadyl(II) complexes of orotic acid and six different amino acids (isoleucine, threonine, proline, phenylalanine, lysine, and glutamine) have been synthesized. Vanadyl(II) orotate mixed ligand complexes are studied on the basis of conductivity, FTIR, UV-Vis, TG-DTG-DTA, magnetic moments, solid powder XRD, SEM, and TEM measurements. These non-electrolyte complexes are of 1 : 1 : 1 stochiometry. The major goal of this article is design and synthesis of new insulin alternative anti-diabetic drug. The insulin hormone and blood glucose level, lipid profile, liver and kidney functions, and superoxide dismutase antioxidant (SOD) are the factors to identify efficiency of the new synthesized compounds as antidiabetic drug agents.
Synthesis of Biaryl Derivatives of Spirofurochromanone in Water and Their Anticancer Activity
Abstract
Biaryl derivatives of spirofurochromanones have been synthesised from 4-bromophenyl derivatives of spirofurochromanones upon catalysis by Pd/C in water. Structures of the synthesised compounds are derived from IR, NMR and HRMS spectral data. The compounds have been tested for in vitro cytotoxicity supported by docking studies.
Extraction-Chromogenic System for Silver(I) Based on Tetrazolium Violet and Semicarbazide Hydrochloride
Abstract
In the presence of semicarbazide hydrochloride (SCH) and traces of AgI, the tetrazolium salt 2,5-diphenyl-3-(1-naphmyl)-2H-tetrazolium chloride (Tetrazolium violet, TV) is reduced in alkaline medium to intensely colored chloroform-extractable 3,5-diphenyl-1-(1-naphthyl)formazan (Tetrazolium violet formazan, TVF). The following experimental parameters have been examined for finding optimal conditions for color development and extraction-spectrophotometric determination of AgI: concentration of reagents, extraction time, volume of the two phases, presence of dissolved oxygen, and light. Under the optimal conditions (cTV = 4.0 × 10−5 mol/dm3, cSCH = 2.4 × 10−3 mol/dm3, cNaOH = 4 × 10−1 mol/dm3, Vaq.phase = 25 cm3, Vchloroform = 4 cm3, extraction time t = 5 min) an isomer of TVF with λmax = 511–512 nm is predominantly extracted. The calibration curve (at 512 nm) is linear in the concentration range of 0.013–0.028 µg cm−3 of AgI. The following ions do not interfere in determination of 0.65 µg of AgI; Li+, Na+, K+, \(\rm{NH}_4^+\), \(\rm{H}_2PO_4^-\), F−, Cl−, \(\rm{SO}_4^{2-}\), \(\rm{B}_4O_7^{2-}\), \(\rm{ReO}_4^-\), tartrate, and citrate (5000-fold excess); MgII and EDTA (1000-fold excess); PbII and BaII (500-fold excess); AlIII (300-fold excess); ZnII and CaII (100-fold excess); VV (50-fold excess); HgII, HgI, MoVI and FeIII (25-fold excess); and CuII and WVI (10-fold excess). CrIII interferes in the process at a mass ratio of 1 : 1, however small amount of this cation (1.5-fold excess) can be masked by EDTA.
Letters to the Editor
Reactions of Ethyl 5-Methyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylate with Selected Bases
Abstract
The reactions of 5-methyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylic acid ethyl ester with some bases have been studied. The opening of 1,2,3-thiadiazole ring under the action of potassium tert-butylate in tetrahydrofuran in the presence of methyl iodide has led to the corresponding 4-methylsulfanylethynylfuran derivative. Under the action of potassium carbonate in DMF with an excess of primary amines or morpholine, the starting thiadiazole has formed the corresponding thioamides of furylacetic acid. The reaction of ethyl 5-methyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylate with hydrazine hydrate has led to hydrazinolysis of the ester group without cleavage of the 1,2,3-thiadiazole ring.
Intramolecular 6-endo-dig-Cyclization of Ethyl 5-Aminomethyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylate
Abstract
The reaction of 5-aminomethyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylic acid ethyl ester with bases has given ethyl 5-sulfanylidene-4,5,6,7-tetrahydrofuro[2,3-c]pyridine-2-carboxylate as a result of intramolecular 6-endo-dig-cyclization of thioketene generated in situ with an internal CH2NH2 nucleophile. The obtained ester has been alkylated with iodomethane at the sulfur atom to form ethyl 5-methylsulfanyl-4,7-dihydrofuro[2,3-c] pyridine-2-carboxylate. The Hantzsch reaction with ω-bromoacetophenone has resulted in the formation of 7-ethoxycarbonyl-3-phenylfuro[3,2-d[1,3]thiazolo[3,2-a]pyridin-4-ium bromide.
Alkoxytelluration of Styrene with Tellurium Tetrahalides
Abstract
An efficient synthesis of the earlier unknown trichloro- and tribromo(2-ahkoxy-2-phenylethyl)-λ4-tellanes with yields of 90 to 100% has been developed basing on alkoxytelluration of styrene with tellurium tetrachloride or tetrabromide in the presence of alcohols. The reduction of tellanes in the NaBH4-H2O-THF and Na2S2O5-H2O-C6H6 systems has afforded bis(2-alkoxy-2-phenylethyl)ditellanes in up to 95% yield.
Synthesis of Phosphorus-Containing Acetamidines Bearing Pharmacophoric Fragments
Abstract
The reactions of N-adamant-1-ylketeniminophosphonates with heterocyclic amines (pyrrolidine, morpholine, 2,6-dimethylpiperidine, 4-ethylpiperazine, 5-methyl-1,2,4-triazole-3-thione, 2-phenyltetrazole-5-thione) furnished a series of new non-symmetrical C-phosphonylated acetamidines.
Thermochemistry of Heteroatomic Compounds. Enthalpy of Dissolution and Vaporization of Selected Trimethylsilyl Di- and Tetrathiophosphates
Abstract
Enthalpy of vaporization (ΔvapH°) of trimethylsilyl esters of dithio- and tetratiophosphoric acids (RX)2P(S)SSiMe3 (X = O, S) have been determined from the experimentally determined enthalpies of their dissolution (ΔdissH°) in n-hexane at 296–298 K and the values of molar refraction (MRD) with correction a for the branching of the carbon substituent according to the equation ΔvapH° = ΔdH°(n-hexane) + 4.39 + 1.05(MRD − α). The obtained vaporization values can be used to calculate the heats of formation of similar, thermally unstable, compounds for experimental calorimetry.
Synthesis and Spectral-Luminescent Properties of 2,5-Diaryl-1,3,4-oxadiazoles and Their Chelate Complexes with Cadmium(II)
Abstract
Cyclization of N′-(arylcarbonyl)benzohydrazides in SOCl2 has afforded 2-aryl-5-(4-octyloxyphenyl)-1H-1,3,4-oxadiazoles; the spectral-luminescent properties of the properties have been studied. The obtained cadmium complex based on 2-[5-(4-octyloxyphenyl)-1,3,4-oxadiazol-2-yl]phenol (L2Cd) have exhibited strong violet luminescence.