The study presents the results of obtaining clathrate inclusion complexes of the alkaloid lupinine (Lup) and its 1,2,3-triazole derivative (Lup-T) using the oligosaccharide β-cyclodextrin (β-CD). The structural features of the encapsulated forms of lupinine (Lup) and its derivatives were characterized by molecular modeling, IR spectroscopy, 1H and 13C NMR, as well as two-dimensional 1H-1H (COSY) and 1H-13C (HMBC, HSQC) NMR spectroscopy. A comparative thermal degradation study of lupinine, its triazole derivative, and their inclusion complexes with β-cyclodextrin was performed using differential thermogravimetry (DTG) and differential scanning calorimetry (DSC). The kinetic parameters of the thermal decomposition reactions of lupinine-based substrates at different heating rates, along with the values of apparent activation energy, were calculated using model-free isoconversional methods by Friedman and Ozawa-Flynn-Wall.
The reactions of lupinine alkaloid and its chlorine derivative with cinnamoyl chloride and 2-K-isoindole-1,3-dione were investigated to obtain 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester and 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione, respectively. The optimal conditions for carrying out the aforementioned reactions were determined, taking into account the nature of the solvent and medium. It was established that acylation of the molecule in a benzene medium, in the presence of trimethylamine, resulted in the formation of 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester, with an 82% yield. It was demonstrated that the interaction of chlorolupinine with 2-K-isoindole-1,3-dione under Gabriel reaction conditions resulted in the formation of 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione. The conformer with an axial orientation of the isoindole-1,3-dione substituent was observed to exhibit greater stability than the conformer with an equatorial orientation. The structure of the synthesized compounds was investigated by IR, 1H, and 13C NMR spectroscopy. The use of two-dimensional spectra in COSY (1H-1H) and HMQC (1H-13C) formats enabled the establishment of homo- and heteronuclear interactions, thereby confirming the structure of the compounds under investigation. The values of chemical shifts, multiplet and integrated intensity of 1H and 13C signals in one-dimensional NMR spectra of the novel compounds were determined. The crystal structures of 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester and 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione were elucidated through X-ray analysis.
The article presents results on the synthesis and investigation of the structural features of a number of 1,4-disubstituted 1H-1,2,3-triazole derivatives of the alkaloid lupinine. Lupinine modification reactions have been carried out at the hydroxymethylene group in the C-1 position of the quinolysine backbone. It has been shown that (octahydro-2H-quinolysine-1-ylmethyl)methanesulfonate in high yield (93%) is formed by the in-teraction of lupinine with methanesulfonyl chloride in methylene chloride. Subsequent treatment of this com-pound with sodium azide in dimethylformamide on heating leads to the formation of 1-(azidomethyl)octahydro-2H-quinolysine in 61% yield. It has been found that the reaction of a new azide with terminal alkynes of various nature in the presence of aqueous СuSO4 and sodium ascorbate in dimethylfor-mamide can form the corresponding 4-substituted (1S,9aR)-1-[(1,2,3-triazol-1-yl)methyl]octahydro-1H-quinolysines. New 1,2,3-triazole derivatives of lupinine containing various aryl substituents at the C-4 posi-tion of the triazole ring have been obtained. The high selectivity of the reaction is explained by the action mechanism of the Sharpless catalyst. The spatial structure of the molecules of lupinine methanesulfonate, 4-aryltriazolylmethyl-octahydroquinolysines has been established by X-ray diffraction analysis. X-ray structur-al analysis data of new compounds have been deposited in the form of CIF files at the Cambridge Crystallo-graphic Data Center
The synthesis of some cytisine derivatives was carried out in the work. The article provides the data of quantum-chemical calculation and virtual screening of the alkaloid cytisine derivatives synthesized. At the same time, the reaction centers of the cytisine derivatives molecules were determined. In order to study the reactivity of the derivatives obtained (namely cinnamoylcytisine, lipoylcytisine, and cytisinylisoalantholactone) the quantum-chemical calculations were conducted to determine the energy and charge characteristics of the molecules. The results indicate a sufficient thermodynamic stability of the cinnamoylcytisine and lipoylcytisine molecules. The cytisinylisoalantholactone molecule is not stable according to the results of quantum chemical calculations. The data on the energy values of the frontier molecular orbitals show that, in general, all molecules exhibit electrophilic properties. A bioprediction was implemented using PASS (Prediction of Activity Spectra for Substances) as one of the most efficient and well-known computer program with the aim of detailed study and the probable establishment of the biological activity of the synthesized cytisine derivatives. Based on the results of virtual screening, promising types of alkaloid cytisine derivatives were identified, which are potential sources of original drugs.
This review has been summarized the data on the synthesis of new hybrid derivatives based on alkaloid molecules. At the same time, there have been analyzed methods for obtaining hybrid structures containing fragments of natural compounds molecules in combination with other biologically active plant metabolites, as leading compounds for the development of new pharmacologically valuable agents, with the aim of creating new original drugs. The combination of pharmacophoric residues in one molecule, namely various aromatic and heterocyclic substituents in the nucleoside position of natural alkaloids, opens up new possibilities for both the subsequent chemical modification of the polyfunctional derivatives obtained and their new diverse biological activity. Effective methods of synthesis have been developed on the basis of directed transformations of these compounds (or their precursors). A wide range of pharmaco-logical properties of combined compounds of these series with a combination of low toxicity is promising. Considering that the preparation of combined derivatives based on alkaloid molecules has been insufficiently studied, the targeted synthesis of new com-pounds is of interest both in terms of new medicinespreparation and the development of new methods of organic synthesis, as well as the molecules stereochemistry determination of a new series of compounds.
The article is a brief overview for the current state of engineering education in Kazakhstan and considers the prospects for its further development and implementation, which is due to the need for industrial and innovative development of our state. Kazakhstan, being an industrially developing country, needs qualified engineering personnel, therefore the training of such specialists at a sufficiently high level is a definite problem. It is noted that for its solution it is necessary to modernize existing study programs, train and retrain teaching staff, widely introduce modern educational approaches and technologies. The article discusses various forms of retraining of teachers of engineering disciplines, for example, advanced training courses for university faculty on the basis of additional education departments. Their topics, duration and forms of conducting are very diverse. Nevertheless, existing problems hinder the development of engineering education in our country; for their successful solution, representatives of the Chemistry and Physics& Technics Departments participate in the international project «EngineeriNg educaTors pEdagogical tRaining» (ENTER). This project implements goals aimed at creating an enabling environment in the educational space based on international cooperation between representatives of universities and the organization of Portugal, Estonia, Slovakia, Russia and Kazakhstan. So, it is planned to elaborate three educational programs (i-PETs) for engineering educators with a variable set of modules based on modern technologies (e-learning) and an individual approach. The implementation of the «ENTER» project is a real prospect of improving the status of engineering education and raising the level of engineering educators’ training in our country.
The article is a brief overview for the current state of engineering education in Kazakhstan and considers the prospects for its further development and implementation, which is due to the need for industrial and innovative development of our state. Kazakhstan, being an industrially developing country, needs qualified engineering personnel, therefore the training of such specialists at a sufficiently high level is a definite problem. It is noted that for its solution it is necessary to modernize existing study programs, train and retrain teaching staff, widely introduce modern educational approaches and technologies. The article discusses various forms of retraining of teachers of engineering disciplines, for example, advanced training courses for university faculty on the basis of additional education departments. Their topics, duration and forms of conducting are very diverse. Nevertheless, existing problems hinder the development of engineering education in our country; for their successful solution, representatives of the Chemistry and Physics& Technics Departments participate in the international project "EngineeriNg educaTors pEdagogical tRaining" (ENTER). This project implements goals aimed at creating an enabling environment in the educational space based on international cooperation between representatives of universities and the organization of Portugal, Estonia, Slovakia, Russia and Kazakhstan. So, it is planned to elaborate three educational programs (i-PETs) for engineering educators with a variable set of modules based on modern technologies (e-learning) and an individual approach. The implementation of the "ENTER" project is a real prospect of improving the status of engineering education and raising the level of engineering educators' training in our country.
Lanthanum-magnesium-nickel tellurite with composition of La2MgNiTeO7 was synthesized from La2O3, NiO, TeO2 oxides and MgCO3 with the help of the ceramic technology. The temperature dependences of the isobaric heat capacity of tellurite La2MgNiTeO7 were studied on an IT-S-400 calorimeter using an experimental method of dynamic calorimetry in the range of 298.15-673 K. The operation of the calorimeter was checked by measuring the standard heat capacity of alpha-Al2O3. The specific heat capacities were measured, and then the molar heat capacities of the synthesized tellurite were calculated using them. In the study of the dependence of the heat capacity of tellurite La2MgNiTeO7 on temperature at 423 K, a sharp anomalous lambda-shaped jump was found, probably related to a second-order phase transition. This transition can be associated with cationic redistribution, changes in the coefficient of thermal expansion and magnetic moment, as well as changes in dielectric constant and electrical resistivity. The equation of the temperature dependence of the heat capacity of the compound is derived on the basis of the experimental data, taking into account the phase transition temperature of the second kind. The temperature dependences of the heat capacity C-p(0)(T) and thermodynamic functions, namely, the entropy S-0(T), the enthalpy H-0(T) H-0(298.15) and the reduced thermodynamic potential Phi(xx)(T) were calculated based on the experimental data on heat capacities and the calculated standard entropy value S-0(298.15) in the interval 298.15-673 K. For the first time, the temperature dependences of the dielectric constant and electrical resistance of tellurite La2MgNiTeO7 in the temperature range of 293-483 K were studied on the LCR-800 instrument. There are maxima and minima on the curves of lg epsilon similar to f(T) and lgR similar to f(T), which confirm the lambda-shaped effect on the C-p(0)similar to f(T) curve of a successful compound, related to the second-order phase transition. The data obtained show that the tellurite studied has semiconductor properties.
In this article the interaction of tert.-butyldiamidophosphites with various alkyl halides with a mobile halogen atom, in particular, allyl chloride, benzyl chloride and bromomalonic ester under various conditions was studied. It was established that reactions with benzyl chloride and allyl chloride proceeded according to the classical Arbuzov reaction scheme by quartering the phosphorus atom with the formation of the corresponding benzyl and allyl amidophosphonates as the main reaction products. It was stated that the reaction proceeded ambiguously with the formation of various products mixture. This is due to the structure of the intermediate "quasiphosphonium", which depends on the nature of the solvent: the ionic form predominates in polar solvents, and the pentavalent form predominates in non-polar solvents. In addition it was proved that the direction of the reaction depended on the reaction conditions, namely, the temperature and the solvent nature. It was shown that the reaction with bromomalonic ester proceeded through the initial protonation of the phosphorus atom with the formation of a quasiphosphonium compound, the decomposition of which led to the corresponding tetraethyldiamidophosphorous acid.
In this paper the effect of microwave irradiation power (MW) on the processes of polycondensation of lactic disturbed total internal reflection acid (LA) was studied for the first time. LA polycondensation was carried out in a multimodal reactor in a vacuum while bubbling with nitrogen at powers of 80, 130, 280, 360 and 500 watts. The change in the temperature of the LA sample under conditions of MW as a function of time and irradiation power was determined. Based on the data of 1H NMR and IR spectroscopy, it was suggested that at 80 W the molecules of physically bound water are mainly removed. The formation of lactic acid oligomers (LAO) occurs at a power of 130-280 W along with the removal of water and LA. Complete removal of water from LAO occurs at 360 watts. When LA is heated at MW power of 430 W, the formation and isolation of colorless crystals is observed, which can be classified by the IR spectra as lactide molecules (nu C=O is 1770 cm(-1), nu C-O-C is 1240 cm(-1)). The molecular weight of LAO decreases at a power of 430 W and above. The kinetic curves of LA polycondensation at 130, 280 and 360 W are presented. The process of LA polycondensation at 360 watts is optimal. It was established that the rate of LA dehydration under MW conditions increases by 15-20 times as compared with carrying out the process under normal heating conditions.
Complex oxide phases, namely new double tellurites of holmium with the composition (HoMeTeO4.5)-Te-II (where Me-II - Sr, Ba) were synthesized with the ceramic technology from Ho(II), Te(IV) oxides and carbonates SrCO3, BaCO3 in the range of 800-1200 degrees C. For the first time the structure of tellurites was investigated by X-ray phase analysis. X-ray phase analysis was performed on the DRON-2.0 device. The intensity of the diffraction peaks was estimated on a stable scale. Radiographs of the synthesized powders were indicated by the homology method. The type of syngony, unit cell parameters, radiographic and pycnometric tellurite densities were determined. HoSrTeO4.5: a = 14.50; b = 14.05; c = 9.04 angstrom; rho(roent.) = 3.73; rho(pycn.) = 3.59 +/- 0.04 g/cm(3); HoBaTeO4.5: a = 12.10; b = 5.49; c = 11.49 angstrom; rho(roent.) = 4.07; rho(pycn.) = 3.93 +/- 0.06 g/cm(3). The correctness of the results of indexing radiographs of tellurites is confirmed by the good agreement between the experimental and calculated values of the reciprocal values of the squares of interplanar distances (10(4)/d(2)) and the consistency of the values of X-ray and pycnometric densities. It has been established that holmium tellurites are synthesized in monoclinic syngony and have a perovskite-like structure. Quantum-chemical calculations of the stable geometry of the synthesized tellurites were carried out using the Gaussian-2009 software package with the help of the UFF molecular method. In this case, equilibrium internuclear distances (long bonds) and bond angles are the parameters. Based on the results of quantum chemical calculations, models of the geometric structure of new holmium tellurites are presented.
A complex study of the aerial part of Serratula coronata L. cultivated in the collection area of medicinal plants of the IRPH "Phytochemistry" (Karaganda) in different phases of growth and using the most optimal extraction methods has been carried out. The content of the main active component of ecdysterone (20E) has been studied. Investigation of the seasonal dynamics of ecdysterone distribution under conditions of varying extraction methods shows that its maximum accumulation is observed during the vegetative phase, and the optimal method in this phase is extraction with isobutyl alcohol, the extract of which contains 13.86 % of ecdysterone and the maceration method with 96.2 % ethyl alcohol with a 20E content of 12.03 %, respectively. It is shown that the maceration with 96.2 % ethyl alcohol is technologically optimal, which fully complies with the international standards of good manufacturing practice (GMP) under pharmaceutical production conditions and excludes the use of toxic and expensive isobutyl alcohol solvent. It has been found that the content of ecdysterone from the beginning of vegetation to the final phase goes down, which is confirmed by the data of high-performance liquid chromatography (HPLC). It is assumed that there is an outflow of ecdysterone to the root system, and then its redistribution occurs as the plant develops further with a partial discharge into the soil. Based on the data on the quantitative content of the target component by the HPLC method, it is recommended that for the preparation of the ecdysterone substance of many actoprotective phytopreparations and valuable WS, the preparation of the above-ground biomass of Serratula coronata L. should be carried out during the vegetation phase of this taxon.
The influence of the calculation method and small structural change in the molecule on the results of geometry and other properties of compounds was studied on the example of known antibiotics. The structural, electronic, and thermodynamic properties of penicillin and phenoxymethylpenicillin were calculated using molecular mechanics and quantum mechanics methods. A comparative analysis of penicillin structures based on experimental data and calculations was carried out. A molecular model of the experimental geometry was considered as the starting structure, which was then optimized. The geometric parameters were computed using the Ellinger MM2 force field method, semi-empirical PM6 one, and ab initio Hartree-Fock (HF) method with the Dunning's correlation consistent basis set cc-pVDZ. Although theoretical calculations were carried out in gaseous phase, cc-pVDZ-optimized geometry of the molecules is close to the crystal structure. Some theoretical parameters for optimized structures of the title compounds, such as total electronic energy, zero-point energy, rotational constants and dipole moments were defined by HF method. The electronic properties as HOMO and LUMO energies for both penicillins were calculated. Thermodynamic properties (heat capacity, entropy) of ones were computed by an ab initio method that took into account the correlation effects.
In this work, great attention was paid to identifying the reasons for the absence of practically implemented technologies for processing chrysotile asbestos wastes and searching for new methods for treating wastes with the aim of obtaining magnesium and other useful products of commercial interest. A series of experiments with solutions of ammonium chloride of different concentrations was carried out to study the kinetics of magnesium leaching. The concentration of magnesium leached increases with the concentration of the NH4Cl solution (C-Mg = 0.092M; C-Mg = 0.1M; C-Mg = 0.102M), as well as with the time of the process itself. It was shown that the difference between the leaching rates of magnesium by 3M and 5M NH4Cl solutions was not significant, and it was rather large for 1M and 3M solutions. The study of the thermodynamics of magnesium leaching was carried out with 3 molar solution of ammonium chloride at various temperatures. Graphs of the concentration of leached magnesium versus the leaching time at different temperatures of the ammonium chloride solution were plotted based on the results obtained. Experiments showed that the degree of magnesium leaching from asbestos increased with increasing temperature. The activation energy was calculated, which was equal to 44 kJ. Sediment identification was carried out using a laser-atomic emission spectrometer apparatus. The results of the experiment showed that a certain amount of magnesium, calcium and a small amount of other metals were contained in the obtained precipitates. Admixture of calcium does not affect the properties of the precipitate obtained. Leaching tests carried out with the help of ammonium chloride solution of various concentrations showed that the fibrous structure of asbestos was not destroyed.
The article presents the results of studies carried out at assembling two branches of science such as the chemistry of heterocyclic compounds and the chemistry of step-growth polymerization. 2,4-Dimethyl-3,5-diethoxycarbonylpyrrole (Knorr pyrrole) was synthesized by a series of successive transformations. 2,4-Dimethylpyrrole-3,5-dicarboxylic acid was obtained by Knorr pyrrole hydrolysis, optimal conditions for reaction were chosen. The process was shown to be completed within an hour and a half in an alcohol-alkaline medium. A new polyester based on 2,4-dimethylpyrrole-3,5-dicarboxylic acid and ethylene glycol was synthesized by a polyesterification reaction. The physicochemical characteristics of the polymer obtained were established. Light-scattering method was used to determine the mass-average molar mass of the polyester, which turned out to be equal to 5263. The good convergence of the data calculated and the reproducibility of the experiment for determining the turbidity of dilute polymer solutions by turbidimetric method indicates the reliability of the results. Analysis of the structure and physical and chemical properties of the polymer synthesized suggests that a polyester based on 2,4-dimethylpyrrole-3,5-dicarboxylic acid and ethylene glycol can be used as a component of alkyd resins potentially possessing biological activity.
Modification of road bitumen by introducing multifunctional additives was studied in the article. Local domestic and industrial wastes of polyurethane polymers were used as a raw material for obtaining such additives. In order to determine the optimal conditions for modification and selection of effective reagent for the process the method of probabilistically deterministic of planning of experiment was applied. Optimal parameters of phenolytical modification of mixture of polyurethane elastomers for the purpose of synthesis of additives for road asphalt bitumen blends were found on the basis of the experimental data processing. Comparison between two methods for the preparation of bituminous mixtures allowed concluding that the introduction of the modifier directly at the beginning of the heat treatment of the parent material is more appropriate in the production of modified coal tar bitumen. The carried on tests of physical and mechanical properties of modified coal tar bitumen showed that the use of synthesized modifier allows significantly expanding the range of high performance and ensuring adhesion properties of the road coal tar bitumen. Conceptual scheme of possible production of modified coal tar bitumen by intensive technology was proposed.
There was studied protonation of aminothiazoles of mineral acids of different strength in order to research the basicity of nitrogen atoms of free amino group and nitrogen of thiazole ring. The results obtained showed high ambidentity of 2-amino-4-phenylthiazole and 2-amino-4-oxothiazole associated with a high degree of delocalization of both the lone pair of electrons of the amino group and the thiazole ring nitrogen atom which creates opportunities for chemical modification of the aminoheterocycles with the free amino group and the ring nitrogen atom..omplexing ability of 2-amino-4-oxothiazole with cobalt (II) chloride caused by high degree of basicity of cyclic nitrogen atom was also studied. Key words: aminoheterocycles, aminothiazoles, mineral
This article was first proposed to glycoluril and its derivatives as flame retardants for rubbers. The effect of flame retardants on mechanical properties of rubbers was studied. The degree of fire protection was determined. It was shown that the addition of rubber to tetra-N-methylolglycoluril with a synergistic blend of flame retardants had an excellent degree of fire protection in comparison with a series of fire resistant rubbers.
In the work presented oxyethylidenediphosphonic acid and its ammonium salt were proposed as rubber flame retardants and rubber formulations were elaborated. The effect of the flame retardant additives on the mechanical properties of rubber was studied, and the degree of fire protection was determined. It was shown that the rubber with the addition of oxyethylidenediphosphonic acid had a higher degree of fire resistance compared to the rubber with oxyethylidenediphosphonic acid ammonium salt.
Flame retardant properties of malonic ester phosphorylated derivatives synthesized by the Michaelis-Becker reaction according to the mechanism of nucleophilic substitution at the reverse mixing of reagents were studied. Fire-retardant efficiency of phosphonmalonic ester was investigated by the method of "fire tube" by determining weight loss of wood samples impregnated with the test substance.