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Volume 511, Nº 1 (2023)

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ХИМИЯ

1,3-DEHYDROADAMANTANE AND ITS DERIVATIVES: A VERSATILE SYNTHETIC PLATFORM FOR PREPARATION OF FUNCTIONAL COMPOUNDS WITH A CAGE STRUCTURE. A REVIEW

Моkhоv V., Butоv G., Novakov I.

Resumo

A promising strategy for the synthesis of a functional compounds with framework structure is using of 1,3‑dehydroadamantane (tetracyclo[3.3.1.1.3,7.0.1,3]decane, 1,3-DHA, bridging [3.3.1]propellane) and its derivatives, which are able to restoration of adamantane structure in their reactions. The review provides information on the methods for the synthesis of 1,3-DHA, spectral characteristics, probable intermediates generated from propellanes, and the advantages of using – low-stage syntheses of hardly available adamantine derivatives, atomic precision, and “green chemistry”. The reactions of 1,3-DHA with a wide range of organic compounds are considered, a comparative assessment of its reactivity with respect to CH-, NH-, OH- and SH-acids, as well as arenes, hydantoins, and heterocyclic compounds is carried out. New chemo- and regioselective methods for the one-step introduction of a 1-adamantyl group into the molecules of various substrates are classified. Particular attention is paid to the reactions of 1,3-DHA with various C–H acids, which make it possible to easily form C–CAd bonds to obtain hard-to-reach adamantane derivatives. The influence of pKa of the substrate on the selectivity of the reactions was shown. Low-step methods for the synthesis of new adamantane derivatives, which have shown high activity as hsEH epoxide hydrolase inhibitors and antitumor agents, are described.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):3-36
pages 3-36 views

INFLUENCE OF As2S3 STOICHIOMETRY ON THE OPTICAL TRANSMISSION OF GLASS IN THE SPECTRAL RANGE 5–8 µm

Snopatin G., Skripachev I., Plotnichenko V., Churbanov M.

Resumo

Glassy chalcogenides AVBVI obtained by solidification of high-temperature melts inherit the polymolecular nature of the melt. The influence of this circumstance on the optical properties of glasses is important in connection with the use of optical fibers for fabrication and has not been adequately studied. Bulk samples of high-pure glasses As40 – xS60 + x (0 < x < 5) with the content of metal and silicon impurities less than 0.1‒0.2 ppm wt., carbon, oxygen, hydrogen compounds – no more than 0.5–1 ppm wt. and optical fibers from them were obtained. The IR spectra of bulk samples 12 cm long and optical fibers up to 15 m long were recorded in the spectral range 1000–2000 cm–1. Absorption bands with maxima near 1950, 1805, 1460, and 1320 cm–1, due to the content of superstoichiometric sulfur in glass, were found in the spectra of bulk samples and fibers, and the corresponding values of the extinction coefficients were determined. The results of the study allow us to consider the As2S3 stoichiometry as a factor that significantly affects the optical characteristics of glass.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):37-41
pages 37-41 views

SYNTHESIS OF DEUTERIUM-LABELED SALICYLCARNOSINE

Shevchenko V., Nagaev I., Kulikova O., Myasoedov N.

Resumo

The effect of temperature on the effectiveness of the introduction of deuterium into a new biologically active compound salicylcarnosine (SC) has been studied. Deuterium gas and heavy water were used as a source of deuterium. The synthesis of labeled SC by the solid-phase method at 190°C leads to the production of [D]SC with a yield of 53%, and a deuterium content of about 4.8 atoms per molecule. During isotope exchange with deuterated water, it was shown that after pretreatment of the catalyst at room temperature with deuterium gas, isotope exchange between SC protons and deuterated water occurs more efficiently. [D]SC is formed with a yield of 46% and contains about 7.3 deuterium atoms per molecule. During the preparative synthesis of labeled SC according to this technique at 190°C, the yield of [D]SC was 6070%, with a deuterium content of about 6.2 atoms per molecule. A new technique for activating the inclusion of deuterium in peptides opens up additional opportunities for obtaining highly labelled drugs.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):42-46
pages 42-46 views

ХИМИЧЕСКАЯ ТЕХНОЛОГИЯ

REDOX NANOSTRUCTURING OF BIPOROUS NICKEL (II) SINTERED USING A SPACE HOLDER

Gnedovets A., Zelenskii V., Shustov V., Alymov M.

Resumo

Permeable metallic nickel and ceramic nickel-oxide materials with nanostructured surface and multilevel hierarchical porosity were created by cyclic redox post-treatment of biporous nickel (II) consolidated in the sintering-dissolution process. Additional levels of intraparticle porosity – Kirkendall pores and shrinkage nanopores – were formed during the stages of high-temperature oxidation in air and reduction in hydrogen, respectively.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):47-53
pages 47-53 views

THE TWO-STAGED REDUCTION SELECTIVE NON-CATALYTIC REDUCTION PROCESS OF NITROGEN OXIDES INTHERMAL GENERATION UNIT FLUE GASES

Kulish O., Zaporozhskii K., Orlova M.

Resumo

The basic concern of research presented in the article was a development of selective non-catalytic reduction of nitrogen oxides in thermal generation units flue gases. The results of the experiments of two-staged selective non-catalytic reduction of nitrogen oxides with below-stoichiometric urea injection are described. Higher and more stable reducing efficiency with minimal formation of ammonia in treated gases is showed.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):54-59
pages 54-59 views

LOW-TEMPERATURE deN2O CATALYST BASED ON Co3O4 FOR A SINGLE-REACTOR SCHEME FOR THE REMOVAL OF NITROGEN OXIDES IN NITRIC ACID PRODUCTION

Isupova L., Ivanova Y.

Resumo

Cesium promoted cobalt spinel is promising as a catalyst for the low-temperature decomposition of nitrous oxide for use in the second stage of a single-reactor scheme for complex purification from nitrogen oxides. In this work, the influence of the conditions for the preparation of massive granular and block catalysts based on Co3O4 by extrusion molding has been studied.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):60-67
pages 60-67 views

ESTIMATION OF EFFICIENCY OF OXALIC ACID APPLICATION IN SOLUTION COMBUSTION SYNTHESIS OF CATALYST FOR PRODUCTION OF HYDROGEN AND CARBON FROM METHANE

Kurmashov P., Popov M., Brester A., Ukhina A., Bannov A.

Resumo

In this work, the parameters of catalyst synthesis by solution combustion method using oxalic acid as a reducing agent, were investigated. The catalysts activity in the process of obtaining hydrogen and carbon nanofibers by the catalytic decomposition of methane has been determined. The effectiveness of using this reagent for the preparation of a nickel catalyst (90% Ni/10% Al2O3) that does not require preliminary reduction with hydrogen was shown. Based on the regression analysis, it was found that among the catalyst synthesis parameters, the yields of carbon and hydrogen are most strongly influenced by temperature.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):68-76
pages 68-76 views

ФИЗИЧЕСКАЯ ХИМИЯ

STATE DIAGRAM OF THE ZrO2–SiO2–Al2O3 SYSTEM WITH VISUALIZATION BY COMPUTER 3D-MODEL AND CALCULATION USING THE NUCLEA DATABASE

Vorob’eva V., Zelenaya А., Lutsyk V., Vorozhtcov V., Almjashev V., Stolyarova V.

Resumo

The three-dimensional (3D) computer model of the isobaric phase diagram of the ZrO2–SiO2–Al2O3 system with formation of the ZrSiO4 and Al6Si2O13 compounds is presented. The development of its geometric structure was carried out through the sequential construction of the phase reaction scheme, including all polymorphic transitions in the sub-solidus and the rearrangement of the interaction of binary compounds as well as zirconium and aluminum oxides, its transformation into the scheme of uni- and invariant states in the tabular and graphical (3D) forms, the construction of the prototype, and its transformation into a spatial model of the phase diagram of the real ZrO2–SiO2–Al2O3 system. Features of the isothermal sections and isopleths of the phase diagram of the considered system calculated using the thermodynamic NUCLEA database are discussed in the comparison with the 3D model sections.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):77-87
pages 77-87 views

THE KINETICS OF ESTERIFICATION OF AMMONIUM LACTATE WITH n-BUTANOL

Meshalkin V., Kozlovskiy M., Kozlovskiy R., Kozlovskiy I., Ibatov Y., Voronov M.

Resumo

For the first time, the kinetics of the process of butyl lactate production by the interaction of ammonium lactate with n-butanol in the presence of water in the temperature range of 130–170°C in a closed system was studied as one of the stages of a new complex technology for the production of lactic acid and polylactide. The flow diagram of the process has been established. For the first time, a kinetic model of ammonium lactate esterification with n-butanol was proposed, considering the side formation of lactamide and the catalysis of esterification due to the acidity of lactic acid. The developed kinetic model can be used for mathematical modeling of the butyl lactate synthesis reactor.

Doklady Rossijskoj akademii nauk. Himiâ, nauki o materialah.. 2023;511(1):88-94
pages 88-94 views

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