Pub Date : 2023-10-08DOI: 10.32362/2410-6593-2023-18-4-381-391
A. I. Musin, Yu. G. Borisova, Sh. Sh. Dzhumaev, N. S. Khusnutdinova, G. Z. Raskil’dina, R. M. Sultanova, S. S. Zlotskii
Objectives. To synthesize derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes and evaluate their effect on platelet aggregation and plasma hemostasis. Methods . To determine the qualitative and quantitative composition of the reaction masses, gas chromatography-, chromate mass spectrometry-, and 1H and 13C nuclear magnetic resonance spectrometry methods were used. Results. Derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes were obtained under thermal heating conditions in order to evaluate their effect on platelet aggregation and plasma hemostasis. Conclusions. Derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes were synthesized in high yields. Their effect on platelet aggregation and plasma hemostasis was established.
{"title":"Synthesis and biological activity of 5-acetyl- and 5-hydroxyalkyl1,3-dioxane derivatives","authors":"A. I. Musin, Yu. G. Borisova, Sh. Sh. Dzhumaev, N. S. Khusnutdinova, G. Z. Raskil’dina, R. M. Sultanova, S. S. Zlotskii","doi":"10.32362/2410-6593-2023-18-4-381-391","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-381-391","url":null,"abstract":"Objectives. To synthesize derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes and evaluate their effect on platelet aggregation and plasma hemostasis. Methods . To determine the qualitative and quantitative composition of the reaction masses, gas chromatography-, chromate mass spectrometry-, and 1H and 13C nuclear magnetic resonance spectrometry methods were used. Results. Derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes were obtained under thermal heating conditions in order to evaluate their effect on platelet aggregation and plasma hemostasis. Conclusions. Derivatives of 5-acetyl- and 5-hydroxyalkyl-1,3-dioxanes were synthesized in high yields. Their effect on platelet aggregation and plasma hemostasis was established.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"67 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135197964","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 : 2023-10-08DOI: 10.32362/2410-6593-2023-18-4-355-380
S. A. Durakov, K. T. Egiazaryan, R. S. Shamsiev, V. R. Flid
Objectives . Catalytic processes involving norbornadiene (NBD) and norbornene (NBN) derivatives provide exceptional opportunities for the synthesis of a wide range of carbocyclic hydrocarbons. By significantly expanding this range, it becomes possible to obtain materials offering a wide variety of predictable properties. The aim of the present review is to summarize the latest achievements in the creation of novel processes catalyzed by palladium compounds. Considerable attention is paid to the study of the mechanisms of NBD allylation reactions by a combination of experimental and theoretical methods. Results . Various strategies of the molecular design of palladium catalysts for syntheses based on NBN and NBD are considered. The possibility of implementing various directions of NBD allylation is demonstrated. Factors influencing the direction of the reactions, by which means individual products can be selectively obtained, are discussed. Conclusions . The effective development of new catalytic processes involving NBD and NBN derivatives requires the complex application of synthetic, kinetic, isotopic, and quantum chemical approaches. By combining instrumental and theoretical methods with constant feedback, it becomes possible to optimize the search for original catalytic systems, obtain information about the mechanisms of their action, and influence technological parameters in a targeted manner.
{"title":"Palladium-catalyzed allylation of norbornadiene: Experimental and quantum chemical research","authors":"S. A. Durakov, K. T. Egiazaryan, R. S. Shamsiev, V. R. Flid","doi":"10.32362/2410-6593-2023-18-4-355-380","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-355-380","url":null,"abstract":"Objectives . Catalytic processes involving norbornadiene (NBD) and norbornene (NBN) derivatives provide exceptional opportunities for the synthesis of a wide range of carbocyclic hydrocarbons. By significantly expanding this range, it becomes possible to obtain materials offering a wide variety of predictable properties. The aim of the present review is to summarize the latest achievements in the creation of novel processes catalyzed by palladium compounds. Considerable attention is paid to the study of the mechanisms of NBD allylation reactions by a combination of experimental and theoretical methods. Results . Various strategies of the molecular design of palladium catalysts for syntheses based on NBN and NBD are considered. The possibility of implementing various directions of NBD allylation is demonstrated. Factors influencing the direction of the reactions, by which means individual products can be selectively obtained, are discussed. Conclusions . The effective development of new catalytic processes involving NBD and NBN derivatives requires the complex application of synthetic, kinetic, isotopic, and quantum chemical approaches. By combining instrumental and theoretical methods with constant feedback, it becomes possible to optimize the search for original catalytic systems, obtain information about the mechanisms of their action, and influence technological parameters in a targeted manner.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"52 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135198611","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 : 2023-10-08DOI: 10.32362/2410-6593-2023-18-4-392-407
A. A. Kozlov, A. S. Aksenov, V. A. Dvoretsky, V. R Flid
Objectives. The paper analyzes the results of research into the formation of photonic crystal structures from polymer microspheres and the mechanisms of spectral shifts during selective reflection of non-monochromatic incident radiation from them in the visible and infrared light, as well as the use of polymer microspheres as sensors for detecting chemical substances having similar structures. Results. Research carried out at the Ya.K. Syrkin Department of Physical Chemistry in the Institute of Fine Chemical Technologies of the RTU MIREA is presented. Issues related to the detection of substances with similar chemical structure using sensors based on photonic crystals made of polystyrene microspheres 160–300 nm in size, are considered. Spectral shifts of the reflected radiation from the crystal surface are registered in the visible spectrum when substances in the liquid or gas phase are detected by the crystal surface. Conclusions. The method of electrophoretic deposition of colloidal particles in the form of polymeric microspheres on conducting surfaces can be used to create ordered structures over large areas. However, the detection of individual compounds by the optical method is impossible without controlling the kinetics of spectral shifts of reflected radiation from the surface of photonic colloidal crystals. The spectral characteristics of such radiation are directly related to the particle sizes that determine the period of the crystal lattice. The diffusion of chemical substances into a photonic crystal, which results in a swelling of the particles forming it and a shift in the spectrum of reflected radiation, is determined by a change in the period of the crystal lattice due to a change in the size of these particles A kinetic model of swelling polymer microspheres, which describes the diffusion of substances into porous polymer particles, is proposed. An excess amount of substance deposited on the surface of a photonic crystal above the limit is shown to lead to its degradation, which is manifested in the “fading” of the crystal surface and the concomitant disappearance of narrow peaks of reflected radiation.
{"title":"Chemical sensors based on photonic colloidal crystals","authors":"A. A. Kozlov, A. S. Aksenov, V. A. Dvoretsky, V. R Flid","doi":"10.32362/2410-6593-2023-18-4-392-407","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-392-407","url":null,"abstract":"Objectives. The paper analyzes the results of research into the formation of photonic crystal structures from polymer microspheres and the mechanisms of spectral shifts during selective reflection of non-monochromatic incident radiation from them in the visible and infrared light, as well as the use of polymer microspheres as sensors for detecting chemical substances having similar structures. Results. Research carried out at the Ya.K. Syrkin Department of Physical Chemistry in the Institute of Fine Chemical Technologies of the RTU MIREA is presented. Issues related to the detection of substances with similar chemical structure using sensors based on photonic crystals made of polystyrene microspheres 160–300 nm in size, are considered. Spectral shifts of the reflected radiation from the crystal surface are registered in the visible spectrum when substances in the liquid or gas phase are detected by the crystal surface. Conclusions. The method of electrophoretic deposition of colloidal particles in the form of polymeric microspheres on conducting surfaces can be used to create ordered structures over large areas. However, the detection of individual compounds by the optical method is impossible without controlling the kinetics of spectral shifts of reflected radiation from the surface of photonic colloidal crystals. The spectral characteristics of such radiation are directly related to the particle sizes that determine the period of the crystal lattice. The diffusion of chemical substances into a photonic crystal, which results in a swelling of the particles forming it and a shift in the spectrum of reflected radiation, is determined by a change in the period of the crystal lattice due to a change in the size of these particles A kinetic model of swelling polymer microspheres, which describes the diffusion of substances into porous polymer particles, is proposed. An excess amount of substance deposited on the surface of a photonic crystal above the limit is shown to lead to its degradation, which is manifested in the “fading” of the crystal surface and the concomitant disappearance of narrow peaks of reflected radiation.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"85 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135198850","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 : 2023-10-08DOI: 10.32362/2410-6593-2023-18-4-341-354
A. V. Afineevskii, D. A. Prozorov, T. Yu. Osadchaya, N. E. Gordina
Objectives . To take into account the change in the number of active sites during the adsorptioncatalytic deformation and deactivation of a catalyst surface by means of a catalytic poison when calculating the turnover frequency (TOF) of a hydrogenation catalyst. Methods. The activity was determined by a static method, using a titanium reactor having a volume of 400 mL, an experimental temperature controlled using a liquid thermostat with an accuracy of 0.5 K, with a paddle stirrer rotation speed of 3600 rpm and system hydrogen pressure equal to atmospheric. The consumption of hydrogen used to reduce the model compound was taken into account via the volumetric method. The heats of hydrogen adsorption were determined using a reaction calorimeter with an operating mode close to that of a chemical reactor. After measuring the specific surface area using low temperature nitrogen adsorption, the results were processed using Brunauer–Emmett–Teller theory approximations. Deactivation was carried out by introducing dosed amounts of catalytic poison into the system in titration mode. Results. A kinetic experiment for the reduction of a multiple carbon bond in a sodium maleate molecule using aqueous solutions of sodium hydroxide with additions of monohydric aliphatic alcohols as solvents under conditions of partial deactivation of the catalyst was carried out. The obtained values of heats of hydrogen adsorption on skeletal nickel in the course of the experiment are given. The described approach is used to calculate TOF values taking into account changes in the number of active surface sites during the course of a catalytic reaction and upon the introduction of a deactivating agent. A refined equation for the correct calculation of TOF is proposed along with its mathematical justification. The results of TOF calculations under various assumptions for a number of catalytic systems are shown. Conclusions. When calculating absolute activity values, a change in the number of active sites has a significant effect on the obtained values. The physical meaning of a number of constants in the proposed equation relates the activity of the catalyst to the distribution of hydrogen on its surface in terms of heats of adsorption.
{"title":"Effect of adsorption-catalytic deformation and partial deactivation on the determination of the absolute activity of a liquid phase hydrogenation catalyst","authors":"A. V. Afineevskii, D. A. Prozorov, T. Yu. Osadchaya, N. E. Gordina","doi":"10.32362/2410-6593-2023-18-4-341-354","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-341-354","url":null,"abstract":"Objectives . To take into account the change in the number of active sites during the adsorptioncatalytic deformation and deactivation of a catalyst surface by means of a catalytic poison when calculating the turnover frequency (TOF) of a hydrogenation catalyst. Methods. The activity was determined by a static method, using a titanium reactor having a volume of 400 mL, an experimental temperature controlled using a liquid thermostat with an accuracy of 0.5 K, with a paddle stirrer rotation speed of 3600 rpm and system hydrogen pressure equal to atmospheric. The consumption of hydrogen used to reduce the model compound was taken into account via the volumetric method. The heats of hydrogen adsorption were determined using a reaction calorimeter with an operating mode close to that of a chemical reactor. After measuring the specific surface area using low temperature nitrogen adsorption, the results were processed using Brunauer–Emmett–Teller theory approximations. Deactivation was carried out by introducing dosed amounts of catalytic poison into the system in titration mode. Results. A kinetic experiment for the reduction of a multiple carbon bond in a sodium maleate molecule using aqueous solutions of sodium hydroxide with additions of monohydric aliphatic alcohols as solvents under conditions of partial deactivation of the catalyst was carried out. The obtained values of heats of hydrogen adsorption on skeletal nickel in the course of the experiment are given. The described approach is used to calculate TOF values taking into account changes in the number of active surface sites during the course of a catalytic reaction and upon the introduction of a deactivating agent. A refined equation for the correct calculation of TOF is proposed along with its mathematical justification. The results of TOF calculations under various assumptions for a number of catalytic systems are shown. Conclusions. When calculating absolute activity values, a change in the number of active sites has a significant effect on the obtained values. The physical meaning of a number of constants in the proposed equation relates the activity of the catalyst to the distribution of hydrogen on its surface in terms of heats of adsorption.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"88 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135197838","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 : 2023-10-08DOI: 10.32362/2410-6593-2023-18-4-328-340
A. F. Schmidt, A. A. Kurokhtina, E. V. Larina, N. A. Lagoda
Objectives. To establish details of catalytic systems operation using the kinetic method with no needs for the differentiation of primary experimental kinetic data. Methods . Analysis of the time patterns of differential selectivity and relative reactivity of substrates in parallel or competing reactions was used. Results . For various coupling reactions of aryl halides and nucleophiles, the possibility to obtain the data about the evolution of the catalytic systems and patterns of the changes of catalytically active species under dynamic transformations of several active and inactive catalyst forms was demonstrated. Conclusions . The analysis of the evolution of differential selectivity and relative reactivity under competing or parallel reactions is the useful tool for discrimination between probable hypotheses of complex catalytic process operation.
{"title":"Analysis of phase trajectories for studying the operational evolution of catalytic systems","authors":"A. F. Schmidt, A. A. Kurokhtina, E. V. Larina, N. A. Lagoda","doi":"10.32362/2410-6593-2023-18-4-328-340","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-328-340","url":null,"abstract":"Objectives. To establish details of catalytic systems operation using the kinetic method with no needs for the differentiation of primary experimental kinetic data. Methods . Analysis of the time patterns of differential selectivity and relative reactivity of substrates in parallel or competing reactions was used. Results . For various coupling reactions of aryl halides and nucleophiles, the possibility to obtain the data about the evolution of the catalytic systems and patterns of the changes of catalytically active species under dynamic transformations of several active and inactive catalyst forms was demonstrated. Conclusions . The analysis of the evolution of differential selectivity and relative reactivity under competing or parallel reactions is the useful tool for discrimination between probable hypotheses of complex catalytic process operation.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"32 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135197986","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 : 2023-10-07DOI: 10.32362/2410-6593-2023-18-4-298-314
K. V. Bozhenko
Objectives . To analyze the history of the development of quantum chemistry and software for quantum chemical calculations in Russia at the Ya.K. Syrkin Department of Physical Chemistry of the M.V. Lomonosov Institute of Fine Chemical Technologies of RTU MIREA. Results. This work presents a historical overview of the development of quantum chemistry at the Ya.K. Syrkin Department of Physical Chemistry from Academician Ya.K. Syrkin to Professor V.R. Flid. It provides a summary of the work with the participation of the author in 1980s–1990s. Quantum-chemical models used to describe some of the intercalation reactions in a bond are considered in comparison with the well-known Woodward–Hoffman and Fukui approaches. The work outlines fundamentals of studies on the design of bifunctional compounds. Conclusions . The physical significance of the exchange interaction constant is given a visual meaning: it establishes the change in spin density on the metals forming complexes of the type in question when passing from isolated cations in the composition of the complexes. The work provides recommendations to synthetic chemists regarding the selection of components in the synthesis of magnetic sublattices of bifunctional materials. It also examines the high level of scientific research carried out at the Ya.K. Syrkin Department of Physical Chemistry and its relevance to the world science level.
{"title":"Regarding certain stages of the development of quantum chemistry in Russia: Experience from the Ya.K. Syrkin Department of Physical Chemistry of the M.V. Lomonosov Institute of Fine Chemical Technologies","authors":"K. V. Bozhenko","doi":"10.32362/2410-6593-2023-18-4-298-314","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-298-314","url":null,"abstract":"Objectives . To analyze the history of the development of quantum chemistry and software for quantum chemical calculations in Russia at the Ya.K. Syrkin Department of Physical Chemistry of the M.V. Lomonosov Institute of Fine Chemical Technologies of RTU MIREA. Results. This work presents a historical overview of the development of quantum chemistry at the Ya.K. Syrkin Department of Physical Chemistry from Academician Ya.K. Syrkin to Professor V.R. Flid. It provides a summary of the work with the participation of the author in 1980s–1990s. Quantum-chemical models used to describe some of the intercalation reactions in a bond are considered in comparison with the well-known Woodward–Hoffman and Fukui approaches. The work outlines fundamentals of studies on the design of bifunctional compounds. Conclusions . The physical significance of the exchange interaction constant is given a visual meaning: it establishes the change in spin density on the metals forming complexes of the type in question when passing from isolated cations in the composition of the complexes. The work provides recommendations to synthetic chemists regarding the selection of components in the synthesis of magnetic sublattices of bifunctional materials. It also examines the high level of scientific research carried out at the Ya.K. Syrkin Department of Physical Chemistry and its relevance to the world science level.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"9 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135302003","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 : 2023-10-07DOI: 10.32362/2410-6593-2023-18-4-315-327315
A. A. Fedorova, O. V. Lefedova, S. A. Shlykov
Objectives. 2-Hydroxy-nitroazobenzenes comprise reagents for the synthesis of heteroaromatic compounds, in the molecules of which the benzene and azole cycles are annulated. These reagents are widely used in the production of chemical products for various industries. In particular, 2-2’-hydroxy-5’-methylphenylbenzotriazole is used as an effective photo stabilizer for polystyrene and polyethylene. A promising method for its preparation is the liquid-phase catalytic hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene (2NAB). The aim of the present study was to establish the structure of 2NAB in solutions of different composition. Methods. Theoretical calculations were carried out within the framework of the density functional theory at a temperature of 298.15 K for the gas phase at B3LYP/6-311++G(d, p) and M06-2X/6-311++G(d, p) levels; for hexane, 2-propanol, toluene at B3LYP/6-311++G(d, p) level using the conductor-like polarizable continuum model. An experimental study to determine the probable isomeric structure of 2NAB in various solvents, including sodium hydroxide (NaOH) and acetic acid (CH3COOH) additives, was carried out using infrared (IR) and ultraviolet (UV) spectroscopy. Results. The most probable structure of 2NAB isomers for the gas phase and a number of solvents was determined. Experimental and theoretical IR and UV spectra were obtained. The thermodynamic characteristics of the reaction of intramolecular proton transfer from –OH to –N=N– group in the gas phase were calculated. Conclusions . A comparison of the experimental and calculated results supports the conclusion that the cis-isomer should be considered most probable for the gas phase. For the studied solutions, a trans-isomer of 2NAB with hydrogen bonds formed between the hydroxyl group hydrogen and the β-nitrogen atom of the azo group of dye molecule should be considered as the most likely structure. In the studied individual and binary solvents, prototropic equilibrium is shifted towards the azo form of the dye, while intramolecular proton transfer is possible only in aqueous diethylamine and dimethylformamide solutions with additions of NaOH.
{"title":"Structure of 2-nitro-2’-hydroxy-5’-methylazobenzene: Theoretical and spectroscopic study","authors":"A. A. Fedorova, O. V. Lefedova, S. A. Shlykov","doi":"10.32362/2410-6593-2023-18-4-315-327315","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-315-327315","url":null,"abstract":"Objectives. 2-Hydroxy-nitroazobenzenes comprise reagents for the synthesis of heteroaromatic compounds, in the molecules of which the benzene and azole cycles are annulated. These reagents are widely used in the production of chemical products for various industries. In particular, 2-2’-hydroxy-5’-methylphenylbenzotriazole is used as an effective photo stabilizer for polystyrene and polyethylene. A promising method for its preparation is the liquid-phase catalytic hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene (2NAB). The aim of the present study was to establish the structure of 2NAB in solutions of different composition. Methods. Theoretical calculations were carried out within the framework of the density functional theory at a temperature of 298.15 K for the gas phase at B3LYP/6-311++G(d, p) and M06-2X/6-311++G(d, p) levels; for hexane, 2-propanol, toluene at B3LYP/6-311++G(d, p) level using the conductor-like polarizable continuum model. An experimental study to determine the probable isomeric structure of 2NAB in various solvents, including sodium hydroxide (NaOH) and acetic acid (CH3COOH) additives, was carried out using infrared (IR) and ultraviolet (UV) spectroscopy. Results. The most probable structure of 2NAB isomers for the gas phase and a number of solvents was determined. Experimental and theoretical IR and UV spectra were obtained. The thermodynamic characteristics of the reaction of intramolecular proton transfer from –OH to –N=N– group in the gas phase were calculated. Conclusions . A comparison of the experimental and calculated results supports the conclusion that the cis-isomer should be considered most probable for the gas phase. For the studied solutions, a trans-isomer of 2NAB with hydrogen bonds formed between the hydroxyl group hydrogen and the β-nitrogen atom of the azo group of dye molecule should be considered as the most likely structure. In the studied individual and binary solvents, prototropic equilibrium is shifted towards the azo form of the dye, while intramolecular proton transfer is possible only in aqueous diethylamine and dimethylformamide solutions with additions of NaOH.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"52 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135301096","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 : 2023-10-07DOI: 10.32362/2410-6593-2023-18-4-287-297287
A. V. Grashkina, V. R. Flid
Objectives . To review the prerequisites for the origin of physical chemistry at the turn of the 19th–20th centuries and to evaluate the contribution of the Department of Physical Chemistry at the M.V. Lomonosov Institute of Fine Chemical Technologies in the development of the main areas of chemical science. Results . The study considers the historical retrospective of the appearance of the Department of Physical Chemistry at the beginning of the 20th century. The main areas of scientific activity over the past 120 years are shown. Conclusions . The Department of Physical Chemistry has made a significant contribution to the formation of physical and chemical knowledge among specialists in wide areas of chemical science and chemical technology. The Department of Physical Chemistry through its pedagogical and scientific activities maintains and expands the areas development, based on the unity of theory and practice, established by its founders. The decisive role of fundamental research in the development of new technologies is also shown.
{"title":"Department of Physical Chemistry in M.V. Lomonosov Institute of Fine Chemical Technologies at the RTU MIREA: From the beginning to the present","authors":"A. V. Grashkina, V. R. Flid","doi":"10.32362/2410-6593-2023-18-4-287-297287","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-287-297287","url":null,"abstract":"Objectives . To review the prerequisites for the origin of physical chemistry at the turn of the 19th–20th centuries and to evaluate the contribution of the Department of Physical Chemistry at the M.V. Lomonosov Institute of Fine Chemical Technologies in the development of the main areas of chemical science. Results . The study considers the historical retrospective of the appearance of the Department of Physical Chemistry at the beginning of the 20th century. The main areas of scientific activity over the past 120 years are shown. Conclusions . The Department of Physical Chemistry has made a significant contribution to the formation of physical and chemical knowledge among specialists in wide areas of chemical science and chemical technology. The Department of Physical Chemistry through its pedagogical and scientific activities maintains and expands the areas development, based on the unity of theory and practice, established by its founders. The decisive role of fundamental research in the development of new technologies is also shown.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"130 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135301101","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 : 2023-10-07DOI: 10.32362/2410-6593-2023-18-4-287-297
A. V. Grashkina, V. R. Flid
Objectives . To review the prerequisites for the origin of physical chemistry at the turn of the 19th–20th centuries and to evaluate the contribution of the Department of Physical Chemistry at the M.V. Lomonosov Institute of Fine Chemical Technologies in the development of the main areas of chemical science. Results . The study considers the historical retrospective of the appearance of the Department of Physical Chemistry at the beginning of the 20th century. The main areas of scientific activity over the past 120 years are shown. Conclusions . The Department of Physical Chemistry has made a significant contribution to the formation of physical and chemical knowledge among specialists in wide areas of chemical science and chemical technology. The Department of Physical Chemistry through its pedagogical and scientific activities maintains and expands the areas development, based on the unity of theory and practice, established by its founders. The decisive role of fundamental research in the development of new technologies is also shown.
{"title":"Department of Physical Chemistry in M.V. Lomonosov Institute of Fine Chemical Technologies at the RTU MIREA: From the beginning to the present","authors":"A. V. Grashkina, V. R. Flid","doi":"10.32362/2410-6593-2023-18-4-287-297","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-287-297","url":null,"abstract":"Objectives . To review the prerequisites for the origin of physical chemistry at the turn of the 19th–20th centuries and to evaluate the contribution of the Department of Physical Chemistry at the M.V. Lomonosov Institute of Fine Chemical Technologies in the development of the main areas of chemical science. Results . The study considers the historical retrospective of the appearance of the Department of Physical Chemistry at the beginning of the 20th century. The main areas of scientific activity over the past 120 years are shown. Conclusions . The Department of Physical Chemistry has made a significant contribution to the formation of physical and chemical knowledge among specialists in wide areas of chemical science and chemical technology. The Department of Physical Chemistry through its pedagogical and scientific activities maintains and expands the areas development, based on the unity of theory and practice, established by its founders. The decisive role of fundamental research in the development of new technologies is also shown.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"78 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135301999","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 : 2023-10-07DOI: 10.32362/2410-6593-2023-18-4-315-327
A. A. Fedorova, O. V. Lefedova, S. A. Shlykov
Objectives. 2-Hydroxy-nitroazobenzenes comprise reagents for the synthesis of heteroaromatic compounds, in the molecules of which the benzene and azole cycles are annulated. These reagents are widely used in the production of chemical products for various industries. In particular, 2-2’-hydroxy-5’-methylphenylbenzotriazole is used as an effective photo stabilizer for polystyrene and polyethylene. A promising method for its preparation is the liquid-phase catalytic hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene (2NAB). The aim of the present study was to establish the structure of 2NAB in solutions of different composition. Methods. Theoretical calculations were carried out within the framework of the density functional theory at a temperature of 298.15 K for the gas phase at B3LYP/6-311++G(d, p) and M06-2X/6-311++G(d, p) levels; for hexane, 2-propanol, toluene at B3LYP/6-311++G(d, p) level using the conductor-like polarizable continuum model. An experimental study to determine the probable isomeric structure of 2NAB in various solvents, including sodium hydroxide (NaOH) and acetic acid (CH3COOH) additives, was carried out using infrared (IR) and ultraviolet (UV) spectroscopy. Results. The most probable structure of 2NAB isomers for the gas phase and a number of solvents was determined. Experimental and theoretical IR and UV spectra were obtained. The thermodynamic characteristics of the reaction of intramolecular proton transfer from –OH to –N=N– group in the gas phase were calculated. Conclusions . A comparison of the experimental and calculated results supports the conclusion that the cis-isomer should be considered most probable for the gas phase. For the studied solutions, a trans-isomer of 2NAB with hydrogen bonds formed between the hydroxyl group hydrogen and the β-nitrogen atom of the azo group of dye molecule should be considered as the most likely structure. In the studied individual and binary solvents, prototropic equilibrium is shifted towards the azo form of the dye, while intramolecular proton transfer is possible only in aqueous diethylamine and dimethylformamide solutions with additions of NaOH.
{"title":"Structure of 2-nitro-2’-hydroxy-5’-methylazobenzene: Theoretical and spectroscopic study","authors":"A. A. Fedorova, O. V. Lefedova, S. A. Shlykov","doi":"10.32362/2410-6593-2023-18-4-315-327","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-4-315-327","url":null,"abstract":"Objectives. 2-Hydroxy-nitroazobenzenes comprise reagents for the synthesis of heteroaromatic compounds, in the molecules of which the benzene and azole cycles are annulated. These reagents are widely used in the production of chemical products for various industries. In particular, 2-2’-hydroxy-5’-methylphenylbenzotriazole is used as an effective photo stabilizer for polystyrene and polyethylene. A promising method for its preparation is the liquid-phase catalytic hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene (2NAB). The aim of the present study was to establish the structure of 2NAB in solutions of different composition. Methods. Theoretical calculations were carried out within the framework of the density functional theory at a temperature of 298.15 K for the gas phase at B3LYP/6-311++G(d, p) and M06-2X/6-311++G(d, p) levels; for hexane, 2-propanol, toluene at B3LYP/6-311++G(d, p) level using the conductor-like polarizable continuum model. An experimental study to determine the probable isomeric structure of 2NAB in various solvents, including sodium hydroxide (NaOH) and acetic acid (CH3COOH) additives, was carried out using infrared (IR) and ultraviolet (UV) spectroscopy. Results. The most probable structure of 2NAB isomers for the gas phase and a number of solvents was determined. Experimental and theoretical IR and UV spectra were obtained. The thermodynamic characteristics of the reaction of intramolecular proton transfer from –OH to –N=N– group in the gas phase were calculated. Conclusions . A comparison of the experimental and calculated results supports the conclusion that the cis-isomer should be considered most probable for the gas phase. For the studied solutions, a trans-isomer of 2NAB with hydrogen bonds formed between the hydroxyl group hydrogen and the β-nitrogen atom of the azo group of dye molecule should be considered as the most likely structure. In the studied individual and binary solvents, prototropic equilibrium is shifted towards the azo form of the dye, while intramolecular proton transfer is possible only in aqueous diethylamine and dimethylformamide solutions with additions of NaOH.","PeriodicalId":33283,"journal":{"name":"Tonkie khimicheskie tekhnologii","volume":"53 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135302000","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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