Odesa National University Herald. Chemistry最新文献

{"title":"BIOLOGICAL ACTIVITY OF N-{3-[(4-METHYLBENZENE-1- SULFONYL)IMINO]-6-OXOCYCLOHEXA-1,4-DIEN-1-YL}ARYLAMIDES AND THEIR DERIVATIVES","authors":"S. Konovalova, A. Avdeenko, V. Lubenets, O. Komarovska-Porokhnyavets, I. Yakymenko, E. Lysenko","doi":"10.18524/2304-0947.2021.1(77).226136","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.1(77).226136","url":null,"abstract":"N-{3-[(4-Methylbenzene-1-sulfonyl)imino]-6-oxocyclohexa-1,4-dien-1-yl}arylamides and their derivatives were synthesized by the reaction of the corresponding N-(4-oxocyclohexa-2,5-dien-1-ylidene)arylsulfonamides with N-chloramides. The biological activity of the synthesized compounds was studied on test cultures of Escherichia coli 67, Staphylococcus aureus 209-p, Mycobacterium luteum VKM B-868 and fungi Candida tenuis VKM Y-70, Aspergillus niger VKM F-1119 by the method of diffusion of substances into agar on a solid nutrient medium. The degree of activity of the test compounds was determined by the diameter of the zones of inhibition of growth of test cultures of microorganisms. The minimum inhibitory, bactericidal and fungicidal concentrations were determined by the method of serial dilutions of the substance in a liquid nutrient medium. At the studied concentration, the method of diffusion of substances into agar on a solid nutrient medium has shown that these compounds have low activity against bacteria Escherichia coli, Staphylococcus aureus, Mycobacterium luteum and fungi Candida tenuis, Aspergillus niger. The diameters of the zones of inhibition of growth of test cultures of microorganisms were less than 15 mm. In research by the method of serial dilutions of the substance in a liquid nutrient medium, they have been found to have bactericidal and fungicidal activity. The minimum inhibitory concentration of N-{2-hydroxy-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 31.2 μg/ml against bacteria Mycobacterium luteum. The minimum inhibitory concentration of N-{2-hydroxy-3-methyl-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide against fungi Aspergillus niger was 31.2 μg/ml. The minimum bactericidal concentration of N-{2-hydroxy-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 62.5 μg/ml against bacteria Mycobacterium luteum. Minimum fungicidal concentration of N-{3-[(4-methylbenzene-1-sulfonyl)imino]-6-oxocyclohexa-1,4-dien-1-yl}benzamide and N-{2-hydroxy-3-methyl-5-[(4-methylbenzene-1-sulfonyl)amino]phenyl}benzamide was 62.5 μg/ml in action to mold fungi Aspergillus niger.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"36 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78873206","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}

{"title":"SPECTROSCOPIC STUDY OF SALT MELTS OF THE SmF3-CeF3-NaCl-KCl SYSTEM","authors":"V. Zinchenko, O. Ieriomin, I. Stoianova, G. Volchak, N. Chivireva, P. Doga, O. V. Stamikosto","doi":"10.18524/2304-0947.2021.1(77).226135","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.1(77).226135","url":null,"abstract":"Redox interactions between the components of the SmF3-CeF3 and SmF3-CeF3-NaCl-KCl systems have been established by IR transmission spectroscopy, diffuse reflectance electron spectroscopy and luminescence spectroscopy. A significant decrease in the transparency in the IR range of the spectrum was found when passing from the first of the systems to the second, which is explained by an increase in scattering by ultramicrodispersed particles of fluorides in the salt melt. In both systems, the formation of a significant amount of Sm (II) and a decrease in the content of Sm (III) are observed. The change in the valence state of Samarium both during solid-phase heat treatment (1100 °C) and during holding in a salt melt at 700 °C is manifested in the disappearance of some absorption bands, the appearance of new bands, and a gypsochromic shift of the remaining bands. The luminescence spectra exhibit high-intensity emission bands in the 640–740 nm range, which correspond to 5d‑4f electronic transitions in Sm2+ ions. At the same time, the highest intensity is observed in the band corresponding to intracenter 5d‑4f electronic transitions in Ce3+ ions. Apparently, the Ce(IV) compound, formed as a result of the exchange reaction of complex fluoride with a salt melt, volatilizes with subsequent decomposition and does not affect the character of luminescence. On the whole, the luminescence intensity after treatment in the molten salt increases by several tens of times, which indicates a significant change in the radiation mechanism. The mechanism of redox reactions in the solid-phase state, as well as exchange processes in the salt melt and after its crystallization, is discussed. A significant role of solvation shells around particles of lanthanide fluorides in luminescence processes is assumed.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82139229","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}

{"title":"CATALYTIC PROPERTIES OF SYNTHETIC HAUSMANNITE IN THE OZONE DECOMPOSITION REACTION","authors":"A. Truba, T. L. Rakitskaya","doi":"10.18524/2304-0947.2021.1(77).226025","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.1(77).226025","url":null,"abstract":"Samples of IS-Mn and IIS-Mn were synthesized and characterized by X-ray diffraction, IR spectroscopy and pH-metry. The X-ray diffraction method revealed both samples to be crystalline and single-phase. IS-Mn sample contains a phase of gausmannite (Mn3O4) with the parameters of the crystal lattice of tetragonal symmetry and the crystallites sized 43 nm. IIS-Mn sample, obtained by calcination of Mn3O4 sample in air under the condition of 600 oC for 4 hours, contains a phase of bixbyite Mn2O3 with a cubic crystal lattice and the crystallites sized 66 nm. The spectra of the Mn3O4 and Mn2O3 samples are particularly different in the region of Mn-OH and Mn-O valence vibrations. For gausmannite, the absorption band for Mn2+ in Td-coordination at 631 cm-1 and the absorption band for Mn3+ in Oh-coordination at 523 and 407cm-1 were clearly shown. In the IR spectrum of bixbyite, several intense absorption bands were observed at 674; 658; 606 and 542 cm-1, which correlate with the literature data and correspond to the valence oscillations of Mn-O in Mn2O3. The pH measurement of the aqueous suspension of the synthesized samples showed that Mn3O4 forms an alkaline medium, and Mn2O3 –weakly acidic upon contact with water molecules. Testing of Mn3O4 and Mn2O3 samples in the ozone decomposition reaction at the initial concentration of 100 mg/m3 showed that the kinetic curves profiles were determined by the phase composition. The testing of the samples was completed and it was established that the same degree of ozone decomposition, namely 50%, was achieved. For hausmannite, the values of the ozone half-life (t1/2) and the amount of ozone (Qexp), which reacted at the end of the experiment, are greater than Mn2O3 sample. The presence of manganese in two oxidation states Mn2+ and Mn3+ in the Mn3O4 structure promotes the redox process, and the alkaline medium contributes to the radical-chain reaction, which affects values t1/2 of and Qexp, which reacted.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80538321","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}

{"title":"HYDROGEN BONDS IN THE FORMATION OF COPPER(II) 1,10-PHENANTHROLINE HYDROXYCARBOXYLATOGERMANATE CRYSTALS USING HIRSHFELD SURFACE ANALYSIS","authors":"E. Chebanenko, O. Buchko, E. Afanasenko, I. Seifullina, E. Martsinko","doi":"10.18524/2304-0947.2021.1(77).226142","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.1(77).226142","url":null,"abstract":"This article is dedicated to the investigation of crystalline structure in the complex cation-anionic compounds Cu(Phen)2Cl]2[Ge(HCit)2]⋅6H2O (I), [Cu(Phen)3]2[Ge2(OH)(HTart)(μ-Tart)2]·11H2O (II), [CuCl(Phen)2]4[{Ge2(OH)2(μ-Tart)2}Cl2]·4Н2О (III), [Cu(Phen)3]2[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (IV), [CuCl(Phen)2]4[(OH)2Ge2(μ-HXylar)4Ge2(μ-OH)2]·8H2O (V) using Hirshfeld surface analysis. This method has showed itself as an effective tool for analysis of intermolecular interactions, such as hydrogen bonds or weaker C…H and С…Н…p connections. Three-dimensional picture of close interactions in the crystal was built for each of the compounds I–V, where short connections are red-colored, while others – weaker and shorter – are light areas and small spots. It was established that in the structures of all compounds different types of hydrogen bonds are presented: bifurcate connections, symmetrical О-Н…О, С-Н…С and asymmetrical ones with water molecules. Two-dimensional histograms – 2D-fingerprint plots, allowed to evaluate quantitively connections in the crystals and establish that H…O/O…H and H…H interactions make the biggest contribution to the total surface area. The presence of the big number of crystallization water molecules is determinant for the formation of complex system of hydrogen bonds and strengthening of the structure, that otherwise would be unstable because of the big size of cations and anions. Due to the fact, that all compounds have the same complexing agent Ge(IV), structure of the anion is determined by polydentate ligand. Obtained results are important for the further development of the water role in the processes of crystallization, crystal formation, electrical dissociation and, especially, dissolving of coordination compounds in biological systems.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"159 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80068296","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}

{"title":"QSPR MODELS FOR ZETA-POTENTIAL OF NANO-OXIDES PREDICTION","authors":"Stelmakh Stelmakh, V. Kuz'min, L. M. Ognichenko","doi":"10.18524/2304-0947.2021.2(78).239101","DOIUrl":"https://doi.org/10.18524/2304-0947.2021.2(78).239101","url":null,"abstract":"Nano-QSPR modeling often requires considering variety of factors, if neglected, may lead to erroneous result of the study. Frequently, the data turned out to be inaccurate, incomplete, or fragmentary. Obviously, the quality of experimental data directly depends on many factors: laboratory equipment, organization of internal regulations, skills of researchers, and so on. As a result of violations of algorithms and protocols of initial data streams processing – there are errors and distortions of data, that is why performing a solid multistep data-curation process is crucial for such procedures. Data curation procedure was performed and approximately 60% was rejected (due to various errors, incomplete or absent records for physicochemical parameters or conditions of performed experiment), followed up by using zeta-potential value dataset for 37 various sizes nanoparticles of 14 metal oxides for calculation of 1D SiRMS descriptors as well as «liquid drop» model cross-descriptors. An efficient consensus model was built (R2 = 0.88, R2test = 0.81). Predictive power (R2 = 0.84) of the model was tested using an external set of 5 nano-oxides and the possibility of satisfactory zeta-potential prediction was shown. Prediction of zeta-potential value within domain applicability of obtained QSPR model confirmed using a Williams plot. The interpretation of the final model was carried out and it was found that the contribution of descriptors was distributed between individual descriptors and cross-descriptors by 46% and 54% respectively. The contribution 1D SiRMS descriptors was 59%, the second group – 41% (liquid drop model descriptors – 29%, descriptors characterizing the metal atom – 12%). It was found that the most influential parameters are the characteristics that reflect the nature of the oxides. The parameters of electrostatic interactions have the highest contribution.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82890595","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}

{"title":"SYNTHESIS AND STRUCTURE OF BINUCLEAR GERMANIUM(IV)-THULIUM(III) COMPLEX WITH 1,3-DIAMINO-2-PROPANOLTETRAACETIC ACID","authors":"E. Martsinko, E. Chebanenko, I. Seifullina, V. Dyakonenko, S. Shishkina","doi":"10.18524/2304-0947.2020.4(76).216921","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.4(76).216921","url":null,"abstract":"New heteronuclear Germanium(IV)- Thulium (III) complex with 1,3-diamino-2-pro- panoltetraacetic acid (H 5 hpdta) was synthesized for the first time. Comparative analysis of IR-spectrum of complex and ligand proved the absence of free COOH-groups in the structure of compound – there are no ν(СООН) absorption bands in the IR-spectra of complex. The significant shift of the ν(С-N) absorption band (about 45 cm -1 ), ν(СН) (about 5 cm -1 ) and presence of ν(Ge-N) and ν(Tm-N) bands evidences that protonized nitrogen atoms form coordination bonds with metals. Two pairs of ν as (СОО) and ν s (СОО) absorption bands of carboxylate ions together with stretching vibrations of Ge-O and Tm-O bonds confirm their coordination to metals. There are also presented ν as (Ge-O-Tm), ν s (Ge-O-Tm), δ (OH міст ) and δ (Ge-OH) absorption bands in the IR-spectrum of complex that indicates the bridging nature of deprotonated hydroxy and hydroxyl group of ligand and also hydrolyzed form of germanium in the structure of compound. During thermal decomposition of the complex in the temperature range of 90-150 ° С as a result of the endothermic effect, two molecules of crystallization water are removed into the gas phase. The further endoeffects at around 150-220° C are seen with the removal of three coordinated water molecules. The oxidative destruction of the complexes is accompanied by the three exoeffects in temperature range 220-800 ° С. The products of final thermal destruction at 1000°C are GeO 2 and Tm 2 O 3 . According to the X-Ray diffraction data of complex [Ge(ОН)( µ -hpdta)( µ -OH) Tm(H 2 O) 3 ] ⋅ 2H 2 O, the six-coordinated atom of Germany and octa-coordinated atom of Thulium are bound by the bridging oxygen atom of hydroxyl group and hydroxyl-anion. The coordination polyhedron of Ge(1) atom is a distorted octahedron formed by three O atoms of deprotonated carboxyl and hydroxyl groups, the nitrogen atom of the hpdta 5– and two O atoms of two hydroxyl-anions. The coordination polyhedron of octa-coordinated atom of Thulium is formed by of the O atoms of deprotonated carboxyl, deprotonated hydroxyl groups of the hpdta 5– , the bridging oxygen atom of hydroxyl-anion, three O atoms of coordinated water molecules and one N-atom of the hpdta 5– .","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74856366","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}

{"title":"SOLVATOCHROMISM OF SOME FOOD AZO DYES","authors":"K. Bevziuk, Y. Bazel, A. Chebotarev, D. Snigur","doi":"10.18524/2304-0947.2020.4(76).216933","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.4(76).216933","url":null,"abstract":"In the current study the solvatochromic properties of such food azo dyes as tartrazine, sunset yellow FCF and carmoisine were described. It was shown that with an increase in the dielectric permittivity of the solvent, a bathochromic shift of the absorption band maxima of azo dyes is observed, which corresponds to the π → π* electronic transition. It has been established that the values of the molar absorptivities of the dominant acid-base form of azo dyes in organic solvents almost linearly (R≈0.90-0.92) increase with an increase in their dielectric permittivity. It is noted that there is a weak correlation (R = 0.70-0.80) between the position of the absorption maximum of the dye and the value of the Hansen parameter.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"63 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84190652","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}

{"title":"SYNTHESIS, FT–IR SPECTROSCOPY AND SURFACE MICROMORPHOLOGY OF Ho(III)–CONTAINING POLYOXOTUNGSTATES","authors":"O. Mariichak, Y. Oleksii, G. M. Rozantsev, S. V. Radio","doi":"10.18524/2304-0947.2020.3(75).211723","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.3(75).211723","url":null,"abstract":"nm. The technique developed in this work for the preparation of sodium decatungstoholmiate(ІІІ) is new and differs in that it allows one to synthesize a normal salt, which can be used for the synthesis of other normal salts of sodium heteropoly decatungstolanthanidates(ІІІ). As a result of attempts to synthesize salts by the interaction of holmium(III) nitrate with aqueous solutions of sodium tungstate acidified to Z = 1.17 and 1.29, X-ray amorphous solids were obtained, which most likely are mixtures of paratungstate B and holmium heptatungstate. Using the methods of chemical analysis and FTIR spectroscopy, the conditions for the formation of a sodium-holmium double salt with lacunar undecatungstate anion, derived from Keggin structure Na 2 Ho 2 [Нo 2 (H 2 O) 10 W 22 O 72 ( OH) 2 ]·46H 2 O are established. Procedure for the synthesis of holmium(III) paratungstate B Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O by the exchange reaction of holmium(ІІІ) nitrate with sodium paratungstate B was elaborated, and by the method of scanning electron microscopy it is proved to be single–phase. It was found that the grain size of the sample is in the range 200–450 nm. The absence of sodium(I) ions in the composition of the synthesized salt was proved by atomic absorption spectroscopy and EDX. Microphotographs of the salt powders Na 9 [Но(W 5 O 18 ) 2 ]·23H 2 O and Ho 10 [W 12 O 40 (OH) 2 ] 3 ·54H 2 O in the characteristic X–ray radiation show no zones with different surface morphologies, and show uniform distribution of Na, Ho, W, O is observed without segregation, which confirms the single–phase nature of the products.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"2012 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86424617","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}

{"title":"AMPHOTERICITY OF OXIDE COMPOUNDS AS A CRITERION AND THE BASIS FOR THE CREATION OF FILM-FORMING MATERIALS","authors":"V. Zinchenko, V. V. Menchuk","doi":"10.18524/2304-0947.2020.3(75).211721","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.3(75).211721","url":null,"abstract":"The question of the quantitative determination of the amphotericity of oxides by the values of their electronegativity is considered. The approximate boundaries of the electronegativity of amphoteric oxides from 1.6 to 2.2 eВ 1/2 /О 2- are established according to the concept of acidity- basicity of Lux-Flood. The possibility of the manifestation of amphoteric properties with a different ratio of acid and basic functions for oxides of the composition MO, M 2 O 3 , MO 2 , M 2 O 5 and MO 3 is analyzed, and the oxides of the composition M 2 O 3 , exhibit the most balanced ratio. The limit values of electronegativity for acid and basic functions are established, which differ by 0.3-0.4 eВ 1/2 /О 2- . The influence of the binary oxide form (oxo-, ortho-, meta-, etc.) on the value of the electronegativity of simple oxides, which they manifest during acid-base interaction, is explained. The influence of the acid-base interaction on the electronegativity of binary oxides at the formation of ternary oxides (complex sulfates, silicates and phosphates) of metals with their equalization and the acquisition of amphoteric properties is shown. The relationship between the electronegativity of simple oxides and their thermal characteristics (melting and boiling points) characterizing the strength of crystal lattices is established. It has been shown that amphoteric oxides having a predominantly covalent crystalline structure have higher thermal parameters than oxides of a predominantly ionic or molecular nature, i.e., basic or acidic oxides. On the other hand, having the most stable crystalline structure, they are less able to chemically interact with environmental components, that is, they have higher climatic stability compared to acidic or basic oxides. This indicates the possible ways of choosing simple oxides as the basis of film-forming materials, as well as creating binary and ternary oxides with the acquisition of amphoteric properties.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"85 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84846945","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}

{"title":"INTERACTION OF 2,4- AND 3,4-BIS(TRIFLUOROACETOXY)BENZOATES WITH SULFUR TETRAFLUORIDE IN ANHYDROUS HYDROGEN FLUORIDE SOLUTION","authors":"I. I. Gaidarzhy, L. A. Motnyak, B. V. Kunshenko","doi":"10.18524/2304-0947.2020.2(74).204384","DOIUrl":"https://doi.org/10.18524/2304-0947.2020.2(74).204384","url":null,"abstract":"Interaction of methyl 3,4-bis(trifluoroacetoxy)benzoate, methyl and ethyl 2,4-bis( trifluoroacetoxy)benzoates with sulfur tetrafluoride in anhydrous hydrogen fluoride solution has been investigated. On the first stage methyl 3,4-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate and ethyl 2,4-dihydroxybenzoate were obtained by esterification of appropriate acids with respective alcohols using concentrated sulfuric acid as a catalyst. On the second stage obtained dihydroxybenzoates were treated with excess of trifluoroacetic anhydride in autoclave at 150 °C for 5 hours. Then, obtained 2,4- and 3,4-bis(trifluoroacetoxy)benzoates were treated with sulfur tetrafluoride in anhydrous hydrogen fluoride solution at 35 °C for 7 hours under continuous stirring. In such conditions methyl 3,4-bis(trifluoroacetoxy)benzoate transforms into methyl 3,4-bis(pentafluoroethoxy)benzoate with high yield. Unexpectedly, methyl and ethyl 2,4-bis(trifluoroacetoxy)benzoate didn’t undergo similar transformations when treated the same way. Instead of respective bis(pentafluoroethoxy)benzoates, methyl and ethyl 2-hydroxy-4-pentafluoroethoxybenzoates were isolated from the reaction mixture. Obviously, fluorination of trifluoroacetoxy group in the 2 position of benzene ring didn’t take place because of the steric hindrance made by ester group, so 4-pentafluoroethoxy-2- trifluoroacetoxy benzoates were formed. The last compounds were turned to 2-hydroxy-4- pentafluoroethoxybenzoates after quenching the reaction mixture with water. Hydrolysis of obtained methyl 3,4-bis(pentafluoroethoxy)benzoate and methyl and ethyl 2-hydroxy-4-pentafluoroethoxybenzoates with water-alcohol alkaline solution and further acidification of reaction mixture with concentrated hydrochloric acid led to the formation of firstly prepared 3,4-bis(pentafluoroethoxy)benzoic and 2-hydroxy-4-pentafluoroethoxybenzoic acids, respectively. The last one is new fluorine-containing analogue of salicylic acid. The molecular mass of the compounds subject to this study was confirmed by EI-MS and GC/ MS analysis.","PeriodicalId":19451,"journal":{"name":"Odesa National University Herald. Chemistry","volume":"36 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80969805","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}