Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5754
L. Mukhtorov, I. Blokhin, Yevgenia V. Ivanova, A. Shumsky, I. Shakhkeldyan, Yu. M. Atroshchenko
A number of new derivatives of N-(3-R-1,5-dinitro-8-oxo-3-azabicyclo[3.3.1]non-6-en-7-yl)acetamides have been synthesized by Mannich condensation of hydride σ-adduct of the N-(2-hydroxy-3,5-dinitrophenyl)acetamide with formaldehyde and primary amines. The synthesis was carried out with two stages. In the first stage, under the action of sodium tetrahydride borate on a solution of N-(2-hydroxy-3,5-dinitrophenyl)acetamide, the C = C bonds of the aromatic ring were reduced to form a 3-charge hydride adduct. The resulting diaduct was isolated from the solution and, while cooling with ice, was introduced into Mannich-condensation with formaldehyde and a solution of the primary amine or amino acid. When the reaction mixture was acidified with dilute orthophosphoric acid to pH 4–5, precipitates of the target products precipitated. After recrystallization from ethanol, the yield of the target products, depending on the substituent at the nitrogen atom, ranged from 55 to 90%. This method is distinguished by relative simplicity, availability of reagents and allows under mild conditions to transfer from the aromatic system activated by nitro groups to 3-azabicyclo[3.3.1]nonane derivatives, containing promising from the point of view of further functionalization nitro, carbonyl and amino groups. The structure of the compounds obtained was proved by IR, 1H-, 13C-, two-dimensional correlation NMR spectroscopy, as well as elemental analysis data. In the IR spectra of the obtained substances, the characteristic absorption bands of amide I (1629-1633 cm-1) and amide II (1560-1570 cm-1), as well as antisymmetric (1549-1556 cm-1) and symmetric (1370-1377 cm-1) oscillations of nitro groups were observed. In the NMR spectra in the weakest field, the broadened signal of the proton NH is observed (δ 9.51-9.57 ppm), followed by the singlet signal of the proton at the double bond (δ 8.15-8.16 ppm). The protons of the methylene groups of the bicyclic system are diastereotopic. Therefore, their signals are mutually split into broadened doublets located in the region of 2.66–3.46 ppm.
{"title":"SYNTHESIS OF NEW DERIVATIVES OF 3-AZABICYCLO[3.3.1]NONANES BASIS ON N-(2-HYDROXY-3,5-DINITROPHENYL)ACETAMIDE σ-ADDUCT","authors":"L. Mukhtorov, I. Blokhin, Yevgenia V. Ivanova, A. Shumsky, I. Shakhkeldyan, Yu. M. Atroshchenko","doi":"10.6060/IVKKT.20186112.5754","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5754","url":null,"abstract":"A number of new derivatives of N-(3-R-1,5-dinitro-8-oxo-3-azabicyclo[3.3.1]non-6-en-7-yl)acetamides have been synthesized by Mannich condensation of hydride σ-adduct of the N-(2-hydroxy-3,5-dinitrophenyl)acetamide with formaldehyde and primary amines. The synthesis was carried out with two stages. In the first stage, under the action of sodium tetrahydride borate on a solution of N-(2-hydroxy-3,5-dinitrophenyl)acetamide, the C = C bonds of the aromatic ring were reduced to form a 3-charge hydride adduct. The resulting diaduct was isolated from the solution and, while cooling with ice, was introduced into Mannich-condensation with formaldehyde and a solution of the primary amine or amino acid. When the reaction mixture was acidified with dilute orthophosphoric acid to pH 4–5, precipitates of the target products precipitated. After recrystallization from ethanol, the yield of the target products, depending on the substituent at the nitrogen atom, ranged from 55 to 90%. This method is distinguished by relative simplicity, availability of reagents and allows under mild conditions to transfer from the aromatic system activated by nitro groups to 3-azabicyclo[3.3.1]nonane derivatives, containing promising from the point of view of further functionalization nitro, carbonyl and amino groups. The structure of the compounds obtained was proved by IR, 1H-, 13C-, two-dimensional correlation NMR spectroscopy, as well as elemental analysis data. In the IR spectra of the obtained substances, the characteristic absorption bands of amide I (1629-1633 cm-1) and amide II (1560-1570 cm-1), as well as antisymmetric (1549-1556 cm-1) and symmetric (1370-1377 cm-1) oscillations of nitro groups were observed. In the NMR spectra in the weakest field, the broadened signal of the proton NH is observed (δ 9.51-9.57 ppm), followed by the singlet signal of the proton at the double bond (δ 8.15-8.16 ppm). The protons of the methylene groups of the bicyclic system are diastereotopic. Therefore, their signals are mutually split into broadened doublets located in the region of 2.66–3.46 ppm.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47084829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5542
Grygoriy A. Ovchinnikov, Valentina А. Gorskikh, Ilyana I. Fassalovа, Vadim S. Тukhvatshin, R. Talipov
In this paper we studied the kinetics of adsorption of 4,4-dimethyl-1,3-dioxane by synthetic zeolites from aqueous solutions in the presence of phosphoric acid. Kinetic mechanism of DMD adsorption from aqueous solutions by synthetic zeolites were considered from the position of three kinetic models: the diffusion model (Boyd and Morris-Weber model), Lagergeren (pseudo-first order), and pseudo-second order. As sorbents we have used synthetic zeolites KA, NaA, CaA, CaX, NaX with a pore diameter of 3-9 Å. DMD (boiling point is 113-114 ºC) was synthesized from isobutylene. Chromatographic analysis was performed on Chromatec Crystal 5000.1 instrument (Russia) using columns (2.0 m in length) with silicone SE-30 (5%) stationary phase (0.16–0.20 mm, operating temperature is 50–220 °C) with nitrogen as a carrier gas. An adsorption of DMD from aqueous solutions was investigated at (75±1) °C from a limited volume under constant mixing (laboratory mechanical stirrer, 17 rps). The contact time of the solution with samples of sorbents varied from 120 to 3600 s. The DMD concentration in solution was determined by the chromatographic method (the internal standard is 4,4,5-trimethyl-1,3-dioxane). The values of the external and internal mass transfer diffusion coefficients were obtained. The effect of the size of zeolite’s pores on the contribution of the external or internal diffusion mass transfer in the process of adsorption of 4,4-dimethyl-1,3-dioxane was founded. The time of establishment of sorption equilibrium was determined. We have found that the process of adsorption of DMD by synthetic zeolites in the presence of phosphoric acid is determined by the values of the diameter of the pores. It is shown that the value of pore diameter of synthetic zeolites does not influence on the аdsorption equilibrium time of DMD. The adsorption equilibrium time for all used family zeolites is 900 s. The kinetics of adsorption of DMD on synthetic zeolites can be correctly described by a pseudo-second-order equation, which indicates the presence of sorbate (DMD) interaction with the sorbent (synthetic zeolite).
{"title":"KINETICS OF ADSORPTION OF 4,4-DIMETHYL-1,3-DIOXANE FROM AQUEOUS SOLUTIONS BY SYNTHETIC ZEOLITES IN PRESENCE OF PHOSPHORIC ACID","authors":"Grygoriy A. Ovchinnikov, Valentina А. Gorskikh, Ilyana I. Fassalovа, Vadim S. Тukhvatshin, R. Talipov","doi":"10.6060/IVKKT.20186112.5542","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5542","url":null,"abstract":"In this paper we studied the kinetics of adsorption of 4,4-dimethyl-1,3-dioxane by synthetic zeolites from aqueous solutions in the presence of phosphoric acid. Kinetic mechanism of DMD adsorption from aqueous solutions by synthetic zeolites were considered from the position of three kinetic models: the diffusion model (Boyd and Morris-Weber model), Lagergeren (pseudo-first order), and pseudo-second order. As sorbents we have used synthetic zeolites KA, NaA, CaA, CaX, NaX with a pore diameter of 3-9 Å. DMD (boiling point is 113-114 ºC) was synthesized from isobutylene. Chromatographic analysis was performed on Chromatec Crystal 5000.1 instrument (Russia) using columns (2.0 m in length) with silicone SE-30 (5%) stationary phase (0.16–0.20 mm, operating temperature is 50–220 °C) with nitrogen as a carrier gas. An adsorption of DMD from aqueous solutions was investigated at (75±1) °C from a limited volume under constant mixing (laboratory mechanical stirrer, 17 rps). The contact time of the solution with samples of sorbents varied from 120 to 3600 s. The DMD concentration in solution was determined by the chromatographic method (the internal standard is 4,4,5-trimethyl-1,3-dioxane). The values of the external and internal mass transfer diffusion coefficients were obtained. The effect of the size of zeolite’s pores on the contribution of the external or internal diffusion mass transfer in the process of adsorption of 4,4-dimethyl-1,3-dioxane was founded. The time of establishment of sorption equilibrium was determined. We have found that the process of adsorption of DMD by synthetic zeolites in the presence of phosphoric acid is determined by the values of the diameter of the pores. It is shown that the value of pore diameter of synthetic zeolites does not influence on the аdsorption equilibrium time of DMD. The adsorption equilibrium time for all used family zeolites is 900 s. The kinetics of adsorption of DMD on synthetic zeolites can be correctly described by a pseudo-second-order equation, which indicates the presence of sorbate (DMD) interaction with the sorbent (synthetic zeolite).","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47326155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5795
N. A. Politaeva, Irina V. Atamanyuk, Yuliya А. Smyatskaya, T. A. Kuznetsova, Toumi Amira, P. Razgovorov
In the present article we introduce application areas of Сhlorella sorokiniana microalgae biomass for national economy (feed and biologically active additives, etc). Here it is shown that thermal and chemical modification of plant material waste might result in obtaining of highly-efficient materials for water purification. Major stages of waste-free technology of microalga processing with further extraction of valuable lipids and obtaining of sorption materials are schematically shown. We have determined fatty-acid content of lipid fraction (77 mg/g), obtained by Soxhlet method from lyophilized microalga biomass. It was revealed, that it includes 83.7% of unsaturated fatty acids (generally, С18:1, С18:2, С18:3), whereas saturated fatty acids are mostly presented by С16 – С20 family. In lyophilized biomass we discovered α-linolenoic acid (Omega-3, 28.3%), which is one of the most valuable biologically active compounds, required for full-value human life and activities. Microstructure analysis of residual biomass of C. sorokiniana microalgae has shown pore surface, formed by destroyed cells. In the course of studying the sorption properties of residual biomass with the use of initial and final concentration parameters, the efficiency of purification of model water from Fe3+ ions (47.5%) was evaluated, which indicates the need to modify the sorption properties of biomass. It has been established that the degree of wastewater purification containing iron (III) compounds can be significantly increased (by 1.8 times) by forming from the residual biomass granular materials with additional introduction of chitosan in the composition, which using as a binder and a modifying additive (mass ratio 4:1).
{"title":"WASTE-FREE TECHNOLOGY OF CHLORELLA SOROKINIANA MICROALGAE BIOMASS USAGE FOR LIPIDS AND SORBENTS PRODUCTION","authors":"N. A. Politaeva, Irina V. Atamanyuk, Yuliya А. Smyatskaya, T. A. Kuznetsova, Toumi Amira, P. Razgovorov","doi":"10.6060/IVKKT.20186112.5795","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5795","url":null,"abstract":"In the present article we introduce application areas of Сhlorella sorokiniana microalgae biomass for national economy (feed and biologically active additives, etc). Here it is shown that thermal and chemical modification of plant material waste might result in obtaining of highly-efficient materials for water purification. Major stages of waste-free technology of microalga processing with further extraction of valuable lipids and obtaining of sorption materials are schematically shown. We have determined fatty-acid content of lipid fraction (77 mg/g), obtained by Soxhlet method from lyophilized microalga biomass. It was revealed, that it includes 83.7% of unsaturated fatty acids (generally, С18:1, С18:2, С18:3), whereas saturated fatty acids are mostly presented by С16 – С20 family. In lyophilized biomass we discovered α-linolenoic acid (Omega-3, 28.3%), which is one of the most valuable biologically active compounds, required for full-value human life and activities. Microstructure analysis of residual biomass of C. sorokiniana microalgae has shown pore surface, formed by destroyed cells. In the course of studying the sorption properties of residual biomass with the use of initial and final concentration parameters, the efficiency of purification of model water from Fe3+ ions (47.5%) was evaluated, which indicates the need to modify the sorption properties of biomass. It has been established that the degree of wastewater purification containing iron (III) compounds can be significantly increased (by 1.8 times) by forming from the residual biomass granular materials with additional introduction of chitosan in the composition, which using as a binder and a modifying additive (mass ratio 4:1).","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47152190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5846
A. E. Pogonin, G. Gamov, M. Zavalishin, V. Sharnin
The hydrazones derived from pyridoxal or pyridoxal 5’-phosphate and heterocyclic hydrazides are of interest due to their potential biological activity and metal sensing properties. These characteristics of hydrazones could be dependent on the conformation equilibria of molecule since the most stable conformer could differ from the one with the highest affinity towards biomolecule or metal ion. In the present contribution, deprotonated hydrazone formed by pyridoxal 5’-phosphate and isoniazid (PLP-INH3-) was studied by means of quantum chemistry. Three rotations leading to eight conformers are possible for this hydrazone; however, four of those species obtained by rotation of pyridine ring of isoniazid residue are degenerated. The geometry of different non-degenerated rotation conformers of the hydrazine (differing by the mutual arrangement of carbonyl group of the isoniazid residue and oxygen in 3’-site of PLP moiety) was optimized using density functional theory (B3LYP/6-311++G(d,p)). Activation barriers were evaluated. Changes in energy and geometry of conformers as well as transition states are discussed. Quantitative QTAIM (Quantum Theory of Atoms in Molecules) analysis was performed in order to check the intermolecular hydrogen bonding existence. The species capable of forming the complex with the metal ions differs from the most stable (according to the total energy values) conformer. The preliminary prediction of biological activity of PLP-INH3- hydrazone and the docking for the hydrazone and G-protein-coupled receptor kinase were performed and the preferable conformation for ligand binding to the kinase active site was found.
吡哆醛或5 ' -磷酸吡哆醛衍生的腙类化合物和杂环肼类化合物因其潜在的生物活性和金属传感特性而受到广泛关注。腙的这些特性可能取决于分子的构象平衡，因为最稳定的构象可能不同于对生物分子或金属离子具有最高亲和力的构象。本文用量子化学方法研究了5′-磷酸吡哆醛与异烟肼(PLP-INH3-)形成的去质子化腙。该腙可以旋转三次得到八个构象;然而，由异烟肼残基吡啶环旋转得到的这些物质中有4个是退化的。利用密度泛函理论(B3LYP/6-311++G(d,p))优化了不同的肼非简并旋转构象(异烟肼残基羰基与PLP部分3′位氧的相互排列不同)的几何形状。对激活屏障进行了评估。讨论了构象的能量和几何形状以及过渡态的变化。为了验证分子间氢键的存在，进行了QTAIM (Quantum Theory of Atoms in Molecules)定量分析。能够与金属离子形成络合物的种类不同于最稳定的(根据总能量值)构象。对PLP-INH3-腙的生物活性进行了初步预测，并与g蛋白偶联受体激酶进行了对接，找到了配体结合激酶活性位点的较优构象。
{"title":"CONFORMATIONAL BEHAVIOR OF HYDRAZONE DERIVED FROM PYRIDOXAL 5’-PHOSPHATE AND ISONIAZID","authors":"A. E. Pogonin, G. Gamov, M. Zavalishin, V. Sharnin","doi":"10.6060/IVKKT.20186112.5846","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5846","url":null,"abstract":"The hydrazones derived from pyridoxal or pyridoxal 5’-phosphate and heterocyclic hydrazides are of interest due to their potential biological activity and metal sensing properties. These characteristics of hydrazones could be dependent on the conformation equilibria of molecule since the most stable conformer could differ from the one with the highest affinity towards biomolecule or metal ion. In the present contribution, deprotonated hydrazone formed by pyridoxal 5’-phosphate and isoniazid (PLP-INH3-) was studied by means of quantum chemistry. Three rotations leading to eight conformers are possible for this hydrazone; however, four of those species obtained by rotation of pyridine ring of isoniazid residue are degenerated. The geometry of different non-degenerated rotation conformers of the hydrazine (differing by the mutual arrangement of carbonyl group of the isoniazid residue and oxygen in 3’-site of PLP moiety) was optimized using density functional theory (B3LYP/6-311++G(d,p)). Activation barriers were evaluated. Changes in energy and geometry of conformers as well as transition states are discussed. Quantitative QTAIM (Quantum Theory of Atoms in Molecules) analysis was performed in order to check the intermolecular hydrogen bonding existence. The species capable of forming the complex with the metal ions differs from the most stable (according to the total energy values) conformer. The preliminary prediction of biological activity of PLP-INH3- hydrazone and the docking for the hydrazone and G-protein-coupled receptor kinase were performed and the preferable conformation for ligand binding to the kinase active site was found.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44702759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5850
Olga E. Nisina, S. V. Lanovetskiy, O. Kosvintsev
When enriching potassium-magnesium ores, millions of tons of solid halite waste are formed, occupying vast areas and posing a danger to the environment. The main useful component of both these wastes is sodium chloride, which serves as a raw material in many chemical industries. The most common processing lines are the production of technical sodium chloride and technical sodium chloride solution. These products are intermediate and can be used in further chemical processes. Obtaining these products of the required quality is hindered by the presence of impurities, such as CaSO4, MgCl2, insoluble residues. The most undesirable impurity is calcium sulphate, the concentration of which can reach 3%. According to the literature sources, the optimal intensity of ultrasonic treatment of the water-dispersed medium was determined. The results of analyzes of phase and granulometric composition of solid halite waste (quarry salt and halite dump) are presented. The character of distribution of calcium sulfate impurity in crystals of halite waste is revealed. The article examines the results of the study of the influence of the intensity of ultrasonic treatment on the residual content of calcium sulphate in halite waste. Based on the results of the studies, the duration and intensity of the ultrasonic effect were established, at which the minimum concentration of calcium sulfate in the resulting halite raw material is reached. The obtained results allowed to establish the optimal regime of the process of cleaning the halite raw materials (intensity of ultrasonic action, processing time), which allow to significantly reduce the content of calcium sulphate during the mechanical cleaning stage and confirmed the potential possibility of using the obtained results for improving the technology of sodium chloride technical solution production, solid halite waste produced by potassium chloride "Uralkali".
{"title":"INFLUENCE OF INTENSITY OF ULTRASONIC ACTION ON DEGREE OF PURIFICATION OF HALITE WASTE FROM CALCIUM SULPHATE IMPURITY","authors":"Olga E. Nisina, S. V. Lanovetskiy, O. Kosvintsev","doi":"10.6060/IVKKT.20186112.5850","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5850","url":null,"abstract":"When enriching potassium-magnesium ores, millions of tons of solid halite waste are formed, occupying vast areas and posing a danger to the environment. The main useful component of both these wastes is sodium chloride, which serves as a raw material in many chemical industries. The most common processing lines are the production of technical sodium chloride and technical sodium chloride solution. These products are intermediate and can be used in further chemical processes. Obtaining these products of the required quality is hindered by the presence of impurities, such as CaSO4, MgCl2, insoluble residues. The most undesirable impurity is calcium sulphate, the concentration of which can reach 3%. According to the literature sources, the optimal intensity of ultrasonic treatment of the water-dispersed medium was determined. The results of analyzes of phase and granulometric composition of solid halite waste (quarry salt and halite dump) are presented. The character of distribution of calcium sulfate impurity in crystals of halite waste is revealed. The article examines the results of the study of the influence of the intensity of ultrasonic treatment on the residual content of calcium sulphate in halite waste. Based on the results of the studies, the duration and intensity of the ultrasonic effect were established, at which the minimum concentration of calcium sulfate in the resulting halite raw material is reached. The obtained results allowed to establish the optimal regime of the process of cleaning the halite raw materials (intensity of ultrasonic action, processing time), which allow to significantly reduce the content of calcium sulphate during the mechanical cleaning stage and confirmed the potential possibility of using the obtained results for improving the technology of sodium chloride technical solution production, solid halite waste produced by potassium chloride \"Uralkali\".","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46550409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5735
A. N. Evdokimov, A. V. Kurzin, A. A. Sivakov, V. S. Golikova
The published data on the solubilities of lithium, sodium, potassium, rubidium and cesium carbonates; sodium bicarbonate; sodium sulphide; potassium and sodium cyanides; orthophosphates, hydro- and dihydroorthophosphates of potassium and sodium, as well as sodium pyrophosphate in methanol, ethanol, 2-propanol, 2-methyl-1-propanol, benzyl alcohol, ethylene glycol, methyl cellosolve and glycerol have been considered and collected. A little bit information for salts has been taken from the most common solubility handbooks, but most of data was selected from scientific articles. There is an acid-base equilibrium with the formation of the corresponding alcoholates in the systems "potassium or sodium carbonate/methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether", "sodium sulphide/methanol, ethanol, 2-propanol, 2-methyl-1-pro-panol, benzyl alcohol", "potassium cyanide/methanol, ethylene glycol, glycerol", "potassium or sodium orthophosphate/ethylene glycol", and "sodium pyrophosphate/ethylene glycol". The mechanism of the reaction of alcoholysis and the formation of alcoholates from the alkali metal salts and alcohols is based on the distribution of the components in phases. Analysis of all phases in the alcohol solutions of alkali metal salts proved the presence of an alcoholysis reaction in some salt/alcohol systems. The concentrations of dissolved salts in alcoholate-generating systems are significantly lower than those determined by the gravimetric method without taking into account the alcoholysis reaction and are considered in the common handbooks "solubilities of the corresponding salts in alcohols". A classification of inorganic alkali metal salts reacting with alcohols in the alcoholysis reaction has been proposed. The analysis of literature data showed that along hydroxides and alkali metal salts, the hydrides, organometallic compounds, acetylenides, nitrides, amides (including alkyl amides) as well as azides can react with alcohols to form alkoxides by alcoholysis reaction. Alcoholysis of salts can be considered as a promising method for the production of alkali metal alkoxides in which the salt is used instead of metal or hydroxide.
{"title":"SOLUBILITY IN ALCOHOLS AND ALCOHOLYSIS REACTIONS OF CARBONATES, SULFIDES, CYANIDES, AND PHOSPHATES OF ALKALI METALS","authors":"A. N. Evdokimov, A. V. Kurzin, A. A. Sivakov, V. S. Golikova","doi":"10.6060/IVKKT.20186112.5735","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5735","url":null,"abstract":"The published data on the solubilities of lithium, sodium, potassium, rubidium and cesium carbonates; sodium bicarbonate; sodium sulphide; potassium and sodium cyanides; orthophosphates, hydro- and dihydroorthophosphates of potassium and sodium, as well as sodium pyrophosphate in methanol, ethanol, 2-propanol, 2-methyl-1-propanol, benzyl alcohol, ethylene glycol, methyl cellosolve and glycerol have been considered and collected. A little bit information for salts has been taken from the most common solubility handbooks, but most of data was selected from scientific articles. There is an acid-base equilibrium with the formation of the corresponding alcoholates in the systems \"potassium or sodium carbonate/methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether\", \"sodium sulphide/methanol, ethanol, 2-propanol, 2-methyl-1-pro-panol, benzyl alcohol\", \"potassium cyanide/methanol, ethylene glycol, glycerol\", \"potassium or sodium orthophosphate/ethylene glycol\", and \"sodium pyrophosphate/ethylene glycol\". The mechanism of the reaction of alcoholysis and the formation of alcoholates from the alkali metal salts and alcohols is based on the distribution of the components in phases. Analysis of all phases in the alcohol solutions of alkali metal salts proved the presence of an alcoholysis reaction in some salt/alcohol systems. The concentrations of dissolved salts in alcoholate-generating systems are significantly lower than those determined by the gravimetric method without taking into account the alcoholysis reaction and are considered in the common handbooks \"solubilities of the corresponding salts in alcohols\". A classification of inorganic alkali metal salts reacting with alcohols in the alcoholysis reaction has been proposed. The analysis of literature data showed that along hydroxides and alkali metal salts, the hydrides, organometallic compounds, acetylenides, nitrides, amides (including alkyl amides) as well as azides can react with alcohols to form alkoxides by alcoholysis reaction. Alcoholysis of salts can be considered as a promising method for the production of alkali metal alkoxides in which the salt is used instead of metal or hydroxide.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46947395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/ivkkt.20186112.5784
A. Pyrko
The aim of this work is the synthesis of new tetraheterocyclic compounds of interest as potential biologically active substances that include the isoxazole and chromone moieties in their structure. The synthesis of such compounds was carried out with two stages. By Knoevenagel condensation of 3-methyl-1,2-isoxazol-5(2H)-on with salicylic aldehyde (4Z)-4-(2-hydro-xybenzyliden)-3-methyl-1,2-oxazol-5(4H)-on was obtained. In this reaction an excess of half of the aldehyde equivalent was used to increase the yield of the product. Pyperidine was used as a catalyst. The reaction was carried out by boiling the components in ethyl acetate. The reaction of the resulting benzylidenisoxazole derivative with cyclohexane-1,3-dione or dimedone was performed by boiling the components in ethanol without the use of a catalyst. The interaction mechanism includes heterodiene Dielsa-Aldera condensation followed by dehydration of one water molecule. As a result, 3-methyl-4-(2-hydroxyphenyl-5,6,7,8-tetrahydroisoxazolo[5,4-b]chromene-5(4H)-one and 3,7,7-trimethyl-4-(2-hydroxyphenyl)-5,6,7,8,9-tetrahydroisoxazolo[5,4-b]chromen-5(4H)–one were obtained. Purification of the synthesized compounds was carried out by crystallization from ethanol. All the obtained compounds were characterised by IR 1H NMR and UV spectroscopies. In 1H NMR spectra there are signals of the methyl groups of the isoxazole ring of compounds at 2.26, 2.29, 2.34 ppm respectively. In the UV spectrum of a plane molecule of (4Z)-4-(2-hydroxybenzyliden)-3-methyl-1,2-oxazol-5(4H)-on there is a long-wave absorption maximum (400.9 nm) corresponding to the joint system of conjugated bonds of the isoxazole and aromatic rings. The structures of the obtained compounds were confirmed by high resolution mass-spectrometry analysis. In the spectra of 3-methyl-4-(2-hydroxyphenyl-5,6,7,8-tetrahydroisoxazolo[5,4-b]chromene-5(4H)-one and 3,7,7-trimethyl-4-(2-hydroxyphenyl)-5,6,7,8,9-tetrahydroisoxazolo[5,4-b]chromen-5(4H)–one the[M + Na]+ ion peaks were observed. The presence of fragment peaks [M + Na – CO]+ and [M + Na – CO – H2O]+ confirms the presence of hydroxy and carbonyl groups in the molecules.
{"title":"SYNTHESIS OF 4-(2-HYDROXYPHENYL)-5,6,7,8-TETRAHYDROISOXAZOLO [5,4-B]CHROMENE-5(4H)-ONES","authors":"A. Pyrko","doi":"10.6060/ivkkt.20186112.5784","DOIUrl":"https://doi.org/10.6060/ivkkt.20186112.5784","url":null,"abstract":"The aim of this work is the synthesis of new tetraheterocyclic compounds of interest as potential biologically active substances that include the isoxazole and chromone moieties in their structure. The synthesis of such compounds was carried out with two stages. By Knoevenagel condensation of 3-methyl-1,2-isoxazol-5(2H)-on with salicylic aldehyde (4Z)-4-(2-hydro-xybenzyliden)-3-methyl-1,2-oxazol-5(4H)-on was obtained. In this reaction an excess of half of the aldehyde equivalent was used to increase the yield of the product. Pyperidine was used as a catalyst. The reaction was carried out by boiling the components in ethyl acetate. The reaction of the resulting benzylidenisoxazole derivative with cyclohexane-1,3-dione or dimedone was performed by boiling the components in ethanol without the use of a catalyst. The interaction mechanism includes heterodiene Dielsa-Aldera condensation followed by dehydration of one water molecule. As a result, 3-methyl-4-(2-hydroxyphenyl-5,6,7,8-tetrahydroisoxazolo[5,4-b]chromene-5(4H)-one and 3,7,7-trimethyl-4-(2-hydroxyphenyl)-5,6,7,8,9-tetrahydroisoxazolo[5,4-b]chromen-5(4H)–one were obtained. Purification of the synthesized compounds was carried out by crystallization from ethanol. All the obtained compounds were characterised by IR 1H NMR and UV spectroscopies. In 1H NMR spectra there are signals of the methyl groups of the isoxazole ring of compounds at 2.26, 2.29, 2.34 ppm respectively. In the UV spectrum of a plane molecule of (4Z)-4-(2-hydroxybenzyliden)-3-methyl-1,2-oxazol-5(4H)-on there is a long-wave absorption maximum (400.9 nm) corresponding to the joint system of conjugated bonds of the isoxazole and aromatic rings. The structures of the obtained compounds were confirmed by high resolution mass-spectrometry analysis. In the spectra of 3-methyl-4-(2-hydroxyphenyl-5,6,7,8-tetrahydroisoxazolo[5,4-b]chromene-5(4H)-one and 3,7,7-trimethyl-4-(2-hydroxyphenyl)-5,6,7,8,9-tetrahydroisoxazolo[5,4-b]chromen-5(4H)–one the[M + Na]+ ion peaks were observed. The presence of fragment peaks [M + Na – CO]+ and [M + Na – CO – H2O]+ confirms the presence of hydroxy and carbonyl groups in the molecules.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49392519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/ivkkt.20186112.5730
V. Y. Doluda, A. V. Bykov, M. Sulman, A. I. Sidorov, Natalia V. Lakina, Esfir M. Sulman
The article presents the results of strained hydrocarbons formation study during the catalytic transformation of methanol into hydrocarbons on zeolite H-ZSM-5. The formation of the following strained cyclic compounds was determined: 1,1-dimethylcyclopropane, 1,2-dimethyl-cyclopropane, 1,1,2-trimethylcyclopropane, 1,2,3-trimethylcyclopropane, 1,1,2,2-tetramethylcyclo-propane, 1,1,2 , 3-tetramethylcyclopropane. The non-stationary character of strained cyclic hydrocarbons formation with a pronounced hydrocarbons formation rate maximum and subsequent deactivation of the catalyst was found. The temperature effect on strained hydrocarbons yield was evaluated. Thus, with an increase in the process reaction temperature up to 400 °C, a maximum of strained hydrocarbons accumulation rate was achieved as 8-8.5 g(Hyd)/(kg(Cat)·h) on 350 h of reaction, and a further increase in the reaction temperature leads to a decrease in the strained hydrocarbons accumulation rate. The effect of the methanol feed rate on the strained hydrocarbons formation rate was also studied. An increase in the methanol feed rate from 0.02 ml/min to 0.16 ml/min results in increase in the strained hydrocarbons formation rate up to 37 g (Hyd)/(kg(Cat)·h). The article presents results of H-ZSM-5 physicochemical study used by ammonia chemisorption, nitrogen phisisorption, X-ray photoelectron spectroscopy. Physicochemical studies of catalyst samples after the methanol transformation process to form strained hydrocarbons showed a twofold decrease in the number of acid sites from 1.2 mmol(NH3)/g (sample) to 0.3 mmol (NH3)/g(sample) and a significant decrease in surface area of micropores from 294 m2/g for the initial sample to 16 m2/g for the sample after the reaction. The X-ray diffraction spectroscopy method showed that the composition of the catalysts H-ZSM-5 surface includes carbon, oxygen, silicon and aluminum. Carbon concentration was found to be 4.3 at.% on the surface of the initial catalyst. While the carbon concentration increases up to 14.1 at.% during the reaction. Also oxygen content on the catalysts surface decreases from 59.9 to 53.4 at%, silica concentration decreases from 35.5 to 32.1 at.%. The following indicates the formation of a carbon surface layer over the catalysts.
{"title":"PECULIARITIES OF SMALL STRAINED ALICYCLE COMPOUNDS FORMATION IN CATALYTIC TRANSFORMATION OF METHANOL OVER ZEOLITE H-ZSM-5","authors":"V. Y. Doluda, A. V. Bykov, M. Sulman, A. I. Sidorov, Natalia V. Lakina, Esfir M. Sulman","doi":"10.6060/ivkkt.20186112.5730","DOIUrl":"https://doi.org/10.6060/ivkkt.20186112.5730","url":null,"abstract":"The article presents the results of strained hydrocarbons formation study during the catalytic transformation of methanol into hydrocarbons on zeolite H-ZSM-5. The formation of the following strained cyclic compounds was determined: 1,1-dimethylcyclopropane, 1,2-dimethyl-cyclopropane, 1,1,2-trimethylcyclopropane, 1,2,3-trimethylcyclopropane, 1,1,2,2-tetramethylcyclo-propane, 1,1,2 , 3-tetramethylcyclopropane. The non-stationary character of strained cyclic hydrocarbons formation with a pronounced hydrocarbons formation rate maximum and subsequent deactivation of the catalyst was found. The temperature effect on strained hydrocarbons yield was evaluated. Thus, with an increase in the process reaction temperature up to 400 °C, a maximum of strained hydrocarbons accumulation rate was achieved as 8-8.5 g(Hyd)/(kg(Cat)·h) on 350 h of reaction, and a further increase in the reaction temperature leads to a decrease in the strained hydrocarbons accumulation rate. The effect of the methanol feed rate on the strained hydrocarbons formation rate was also studied. An increase in the methanol feed rate from 0.02 ml/min to 0.16 ml/min results in increase in the strained hydrocarbons formation rate up to 37 g (Hyd)/(kg(Cat)·h). The article presents results of H-ZSM-5 physicochemical study used by ammonia chemisorption, nitrogen phisisorption, X-ray photoelectron spectroscopy. Physicochemical studies of catalyst samples after the methanol transformation process to form strained hydrocarbons showed a twofold decrease in the number of acid sites from 1.2 mmol(NH3)/g (sample) to 0.3 mmol (NH3)/g(sample) and a significant decrease in surface area of micropores from 294 m2/g for the initial sample to 16 m2/g for the sample after the reaction. The X-ray diffraction spectroscopy method showed that the composition of the catalysts H-ZSM-5 surface includes carbon, oxygen, silicon and aluminum. Carbon concentration was found to be 4.3 at.% on the surface of the initial catalyst. While the carbon concentration increases up to 14.1 at.% during the reaction. Also oxygen content on the catalysts surface decreases from 59.9 to 53.4 at%, silica concentration decreases from 35.5 to 32.1 at.%. The following indicates the formation of a carbon surface layer over the catalysts.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42904471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5826
V. Sharutin, O. Sharutina, A. Tkacheva
Potassium tetraethylammonium hexathiocyanatoplatinate(IV) (Et4N)(K)[Pt(SCN)6] (I) was synthesized by the reaction of potassium hexathiocyanatoplatinate(IV) with tetraethylammonium chloride in acetonitrile aqueous solution. Slow evaporation of the solvent led to the formation of large red-brown crystals. The product structure was determined by XRDA. The X-ray diffraction pattern of crystal I was carried out on a Bruker D8 QUEST diffractometer (MoKα radiation, λ = 0.71073 Å, graphite monochromator). [С14H20N7KPtS6, M = 712.92, Crystal system monoclinic, space group C 2/c, a = 10.432(8), b = 14.767(13), c = 16.300(13) Å, V = 2510(4) Å3, Z = 4, µ = 6.272 mm-1, F(000) = 1384, crystal size 0.86×0.66×0.50 mm]. The tetrahedral configuration of the tetraethylammonium cation is slightly distorted (CNC angles are 105.5(5)º-111.8(4)º, bond lengths N-С are 1.503(5)-1.519(5) Å). Platinum ions in anions have octahedral coordination (trans-angles SPtS are 180º, cis-angles SPtS are (88.47(4)º-91.53(4)º). The bond lengths Pt-S are equal to 2.373 (2)-2.37(2) Å. Potassium cations are coordinated by six nitrogen atoms of thiocyanate groups (distances N K (2.828(4)-2.896 (4) Å). Trans-angles NKN (128.44 (15)º-146.9 (2)º) are far from ideal values for the octahedron. Bridged thiocyanate ligands are bonded cations of the platinum and potassium. Ambidentate thiocyanate ligands are simultaneously coordinated to the K+ cation by nitrogen atoms. By means of the bridged thiocyanate ligands a three-dimensional coordination polymer is formed. The resulting structure is a three-dimensional grid, in the cells of which the cations of tetraethylammonium (Et4N)+ are located.
{"title":"SYNTHESIS AND STRUCTURE OF POTASSIUM TETRAETHYLAMMONIUM HEXATHIOCYANATOPLATINATE(IV)","authors":"V. Sharutin, O. Sharutina, A. Tkacheva","doi":"10.6060/IVKKT.20186112.5826","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5826","url":null,"abstract":"Potassium tetraethylammonium hexathiocyanatoplatinate(IV) (Et4N)(K)[Pt(SCN)6] (I) was synthesized by the reaction of potassium hexathiocyanatoplatinate(IV) with tetraethylammonium chloride in acetonitrile aqueous solution. Slow evaporation of the solvent led to the formation of large red-brown crystals. The product structure was determined by XRDA. The X-ray diffraction pattern of crystal I was carried out on a Bruker D8 QUEST diffractometer (MoKα radiation, λ = 0.71073 Å, graphite monochromator). [С14H20N7KPtS6, M = 712.92, Crystal system monoclinic, space group C 2/c, a = 10.432(8), b = 14.767(13), c = 16.300(13) Å, V = 2510(4) Å3, Z = 4, µ = 6.272 mm-1, F(000) = 1384, crystal size 0.86×0.66×0.50 mm]. The tetrahedral configuration of the tetraethylammonium cation is slightly distorted (CNC angles are 105.5(5)º-111.8(4)º, bond lengths N-С are 1.503(5)-1.519(5) Å). Platinum ions in anions have octahedral coordination (trans-angles SPtS are 180º, cis-angles SPtS are (88.47(4)º-91.53(4)º). The bond lengths Pt-S are equal to 2.373 (2)-2.37(2) Å. Potassium cations are coordinated by six nitrogen atoms of thiocyanate groups (distances N K (2.828(4)-2.896 (4) Å). Trans-angles NKN (128.44 (15)º-146.9 (2)º) are far from ideal values for the octahedron. Bridged thiocyanate ligands are bonded cations of the platinum and potassium. Ambidentate thiocyanate ligands are simultaneously coordinated to the K+ cation by nitrogen atoms. By means of the bridged thiocyanate ligands a three-dimensional coordination polymer is formed. The resulting structure is a three-dimensional grid, in the cells of which the cations of tetraethylammonium (Et4N)+ are located.","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44451108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-12-12DOI: 10.6060/IVKKT.20186112.5717
A. Saginayev, E. I. Bagrii
Propyladamantanes were synthesized by alkylation of adamantane with isopropyl alcohol in the temperature range from 5 to 40 °C in the presence of 96% sulfuric acid. Tetramethyl- and dimethylethyladamantanes were synthesized by isomerization of perhydroanthracene in the presence of aluminium oxide catalyst on the setup of the flow type. Isomers of butyladamantanes were obtained by the reaction of alkylation of the adamantane with isooctane. For each molecule, the optimization of the geometric parameters of atoms was carried out using analytical calculation methods. By calculating the frequencies of normal vibrations using the second derivatives, it was confirmed that the stationary points determined by optimizing the geometry correspond to the minima of the potential energy surface. The structure of 1-n-propyladamantane (I), 1-isopropyl-adamantane (II), 2-n-propyladamantane (III), 1,2-di-n-propyladamantane (IV), 1,3-dimethyl-5-ethyladamantane (V), 1,3,5,6-tetramethyladamantane (VI), 1,3,5,7-tetramethyladamantane (VII), perhydroanthracene (VIII), 1-n-butyladamantane (IX), 1-isobutyladamantane (X), 1-sec-butyladamantane (XI) has been studied using the DFT method with the Becke–Lee–Yang–Parr hybrid energy functional of electron density with the 6-31G* basis set. The geometric and electronic characteristics of the compounds and their total energy, normal vibration frequencies have been calculated. It has been shown that the calculated Gibbs free energies of formation for the perhydroanthracene isomerization products are in qualitative agreement with the experimental product composition of the isomerate and alkylation of adamantane with isopropyl alcohol are in qualitative agreement with the experimental composition of the products. A good agreement of calculated and experimental data on the composition of equilibrium mixtures was obtained. The theoretical geometry of the synthesized alkyladamantanes with Td symmetry very well agrees with the results of electron diffraction. Closest to the results obtained experimentally, the geometry was predicted by B3LYP, in which the lengths of C-C and C-H bonds are close to 1.544 and 1,100Ả, respectively, and the C-Csec-C and C-Cter-C angles are 109°. The results of the calculation using the B3LYP method are in good agreement with the experimental data. There is no definite relationship between the size of the molecules and the convergence of the calculated and experimental data. A practically important conclusion arising from the results of this and previous studies is that the use of the calculation method leads to “chemically accurate” data.
{"title":"GEOMETRICAL AND ELECTRONIC STRUCTURE OF PROPYL-, TETRAMETHYL-, DIMETHYLETHYL- AND BUTYLADAMANTANES AND THEIR THERMODYNAMIC CHARACTERISTIC ACCORDING TO DFT","authors":"A. Saginayev, E. I. Bagrii","doi":"10.6060/IVKKT.20186112.5717","DOIUrl":"https://doi.org/10.6060/IVKKT.20186112.5717","url":null,"abstract":"Propyladamantanes were synthesized by alkylation of adamantane with isopropyl alcohol in the temperature range from 5 to 40 °C in the presence of 96% sulfuric acid. Tetramethyl- and dimethylethyladamantanes were synthesized by isomerization of perhydroanthracene in the presence of aluminium oxide catalyst on the setup of the flow type. Isomers of butyladamantanes were obtained by the reaction of alkylation of the adamantane with isooctane. For each molecule, the optimization of the geometric parameters of atoms was carried out using analytical calculation methods. By calculating the frequencies of normal vibrations using the second derivatives, it was confirmed that the stationary points determined by optimizing the geometry correspond to the minima of the potential energy surface. The structure of 1-n-propyladamantane (I), 1-isopropyl-adamantane (II), 2-n-propyladamantane (III), 1,2-di-n-propyladamantane (IV), 1,3-dimethyl-5-ethyladamantane (V), 1,3,5,6-tetramethyladamantane (VI), 1,3,5,7-tetramethyladamantane (VII), perhydroanthracene (VIII), 1-n-butyladamantane (IX), 1-isobutyladamantane (X), 1-sec-butyladamantane (XI) has been studied using the DFT method with the Becke–Lee–Yang–Parr hybrid energy functional of electron density with the 6-31G* basis set. The geometric and electronic characteristics of the compounds and their total energy, normal vibration frequencies have been calculated. It has been shown that the calculated Gibbs free energies of formation for the perhydroanthracene isomerization products are in qualitative agreement with the experimental product composition of the isomerate and alkylation of adamantane with isopropyl alcohol are in qualitative agreement with the experimental composition of the products. A good agreement of calculated and experimental data on the composition of equilibrium mixtures was obtained. The theoretical geometry of the synthesized alkyladamantanes with Td symmetry very well agrees with the results of electron diffraction. Closest to the results obtained experimentally, the geometry was predicted by B3LYP, in which the lengths of C-C and C-H bonds are close to 1.544 and 1,100Ả, respectively, and the C-Csec-C and C-Cter-C angles are 109°. The results of the calculation using the B3LYP method are in good agreement with the experimental data. There is no definite relationship between the size of the molecules and the convergence of the calculated and experimental data. A practically important conclusion arising from the results of this and previous studies is that the use of the calculation method leads to “chemically accurate” data. \u0000 ","PeriodicalId":45993,"journal":{"name":"Izvestiya Vysshikh Uchebnykh Zavedenii Khimiya i Khimicheskaya Tekhnologiya","volume":" ","pages":""},"PeriodicalIF":0.9,"publicationDate":"2018-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44637675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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