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CO_(2)-Free Calcium Carbide Manufacturing: Demanded Strategy in the Carbon-Neutral Chemical Industry

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Chinese Journal of chemistry 2023年第24期41卷 3611-3617页

作者： Dmitriy E.Samoylenko Konstantin S.Rodygin Valentine P.Ananikov institute of chemistry Saint Petersburg State University7/9 Universitetskaya nabSt.Petersburg199034 Russia Zelinsky Institute of Organic Chemistry Russian Academy of SciencesLeninsky pr.47Moscow119991 Russia

Calcium carbide is considered a possible key component in the sustainable carbon cycle,including convenient recycling of carbon wastes to industrial uptake.However,currently employed CaC2 manufacturing process produces significant amounts of CO_(2).One of the main factors of its appearance is the formation of carbon oxide during the reaction.The reaction of lime ore with coal inevitably results in the formation of CO and the loss of one carbon atom.CO is usually burnt,forming CO_(2) to maintain the required high temperature during synthesis – 2200 ℃.In the present study,we discuss that the use of calcium metal instead of lime represents a good opportunity to prevent CO_(2) emission since the reaction of Ca with carbon occurs in an atom-efficient manner and results in only CaC_(2) at a much lower temperature of 1100 ℃.Here,the reaction of Ca with carbon was successfully tested to synthesize CaC_(2).The desired product was isolated in gram-scale amounts in 97.2% yield and 99% purity.The environmental friendliness of the proposed method originates from the calculations of the E-factor.Rationalization is provided concerning the cost factor of Ca within the considered process.

关键词： CO_(2)emission CaC_(2) Carbon cycle Sustainable chemistry Green chemistry

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含能快递

含能材料 2013年第3期21卷 400-408页

作者： Aleksei B.Sheremetev 张光全俄罗斯N.D.Zelinsky Institute of Organic Chemistry

美斯蒂文斯理工学院用聚焦离子束-电镜扫描(FIB-SEM)研究压制PBX的空隙分布近来,美国美国斯蒂文斯理工学院采用聚焦离子束-电镜扫描(FIB-SEM)研究压制PBX的空隙,结合3D成像模型能够立体显示炸药配方中空隙分布。该空隙表征技术还能对纳... 详细信息

美斯蒂文斯理工学院用聚焦离子束-电镜扫描(FIB-SEM)研究压制PBX的空隙分布近来,美国美国斯蒂文斯理工学院采用聚焦离子束-电镜扫描(FIB-SEM)研究压制PBX的空隙,结合3D成像模型能够立体显示炸药配方中空隙分布。该空隙表征技术还能对纳米配方进行表征,通过对一种纳米RDX的压制PBX配方的表征,发现空隙的平均尺寸为250 nm,同时还得到了空隙的体积、形状及其立体分布。

关键词：熔铸炸药含能爆轰性能含能材料

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含能快递

含能材料 2012年第5期20卷 656-660页

作者： Aleksei B.Sheremetev 张光全俄罗斯N.D.Zelinsky Institute of Organic Chemistry

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含能快递(英文)

含能材料 2013年第1期21卷 135-136页

作者： Aleksei B.Sheremetev 俄罗斯N.D.Zelinsky Institute of Organic Chemistry

Estimation of the Ballistic Effectiveness of 3,4-and 3,5-Dinitro-1-(trinitromethyl)-1H-Pyrazoles as Oxidizers for Composite Solid Propellants

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火炸药学报 2016年第2期39卷 16-21页

作者： LEMPERT David B. DALINGER Igor L. SHU Yuan-jie KAZAKOV Anatolii I. SHEREMETEV Aleksei B. institute of Problems of Chemical Physics Russian Academy of Sciences(IPCP RAS) Moscow 142432 Russia Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow 119991 Russia Xi'an Modern chemistry Research institute Xi'an 710065 China

The experimental values of the enthalpy of formation of two isomeric 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles have been obtained(261.5±5.0and 246.4±6.7kJ/mol for crystalline 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles,respectively).The ballistic effectiveness of these potential oxidizers in composite solid propellants was studied.It is shown that these two oxidizers may be successfully applied in metal-free compositions or with a small content of metal.For the bottom stage 3,4-dinitro-1-(trinitromethyl)-1H-pyrazole is a bit better than 3,5-dinitro-1-(trinitromethyl)-1H-pyrazole,for the upper stage the both oxidizers show the equal ballistic parameters.These oxidizers allow to create metal-free solid composite propellants with the binder percentage not lower than 19%(volume fraction),with I3spequal to 256.5-257.0sat density equal to 1.72-1.74g/cm^3.

关键词： composite solid propellants high-enthalpy oxidizer energetic parameters estimation specific impulse ballistic effectiveness

Cobalt-Catalyzed Intermolecular Hydroamination of Unactivated Alkenes Using NFSI as Nitrogen Source

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Chinese Journal of chemistry 2022年第9期40卷 1066-1072页

作者： Peng-Wei Sun Ze Zhang Xinyao Wang Linshan Li Yuxin Li Zhengming Li State Key Laboratory of Elemento-organic chemistry Research Institute of Elemento-Organic ChemistryCollege of ChemistryNankai UniversityTianjin 300071China

Cheap metal(Fe,Mn,and Co)-catalyzed hydroamination of alkenes has been an attractive method for synthesis of amines because of biocompatibility of metal,excellent Markovnikov selectivity and chemoselectivity.However,most reports are limited to unsaturated nitrogen sources(nitric oxide,azos,azides,cyano,etc.),for which aminated products are very limited.Notably,while used widely for fluorinating reaction,N-fluorobenzenesulfonimide(NFsI)as amine source for hydroamination has seldom been reported.Here we developed a cobalt-catalyzed intermolecular hydroamination of unactivated alkenes using NFSl as nitrogen source under mild conditions.The reaction exhibits excellent chemo-and regio-selectivity with no hydrofluorination or linear-selectivity products.Notably,the reaction proceeded with excellent yield even though the amount of Co(salen)catalyst was reduced to 0.2 mol%.Recently,a similar work was also reported by Zhang and coworkers(ref.19).

关键词： Hydroamination Alkenes NFSI Cobalt catalysis Mild conditions

Extended Corey-Chaykovsky reactions:transformation of 2-hydroxychalcones to benzannulated 2,8-dioxabicyclo[3.2.1]octanes and 2,3-dihydrobenzofurans

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organic chemistry Frontiers 2022年第3期9卷 737-744页

作者： Alexander A.Fadeev Anton S.Makarov Olga A.Ivanova Maxim G.Uchuskin Igor V.Trushkov Department of chemistry Perm State UniversityBukireva 15Perm 614990Russian Federation Department of chemistry M.V.Lomonosov Moscow State UniversityLeninskie Gory 1-3Moscow 119991Russian Federation N.D.Zelinsky Institute of Organic Chemistry Leninsky pr.47Moscow 119334Russian Federation. D.Rogachev National Medical Research Center of Pediatric Hematology Oncology and ImmunologySamory Mashela 1Moscow 117997Russian Federation

We report the divergent synthesis of benzannulated 2,8-dioxabicyclo[3.2.1]octanes and 2,3-dihydrobenzofurans using the concept of extended Corey-Chaykovsky reactions.With this concept,2-hydroxychalcones were treated with the Corey ylide providing highly reactive donor-acceptor cyclopropanes that were introduced in a one pot manner for further transformations.

关键词： octane donor

Nitroxy-and azidomethyl azofurazans as advanced energetic materials

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Defence Technology（防务技术） 2022年第8期18卷 1369-1381页

作者： Aleksei B.Sheremetev Svetlana F.Mel'nikova Elizaveta S.Kokareva Ruslan E.Nekrutenko Kirill V.Strizhenko Kyrill Yu Suponitsky Thanh Dat Pham Alla N.Pivkina Valery P.Sinditskii Zelinsky Institute of Organic Chemistry Russian Academy of Sciences47 Leninsky ProspMoscow119991Russia Saint Petersburg State institute of Technology 26 Moskovskii PrSt Petersburg190013Russia Mendeleev University of Chemical Technology Moscow125047Russia N.N.Semenov Federal Research Center for Chemical Physics Russian Academy of Sciences4 Kosygina Str119991MoscowRussia

Progress in the rocket industry is only possible on the basis of new, higher performance and more environmentally friendly materials compared to up-to-date propellant ingredients for liquid, solid, gelled and hybrid propellant systems. In this work, synthetic methods have been developed for the preparation of new energetic azofurazans bearing nitroxymethyl or azidomethyl groups. All prepared compounds were fully characterized by multinuclear NMR and IR spectroscopies, as well as elemental analyses. An analysis of the structural features based on the X-ray single-crystal diffraction made it possible to discuss their influence on the densities of the azofurazans of this study. Thermal decomposition and combustion of nitroxymethyl and azidomethyl azofurazans were studied using a number of complementary experimental techniques, namely thermogravimetry, differential scanning calorimetry, manometry, microthermocouple measurements in the combustion wave. The structural and physical characteristics of these new energetic analogues illustrate the extent to which the nature of the explosophoric groups can be used to tune the performace of the azofurazan framework. These azofurazans possess positive calculated enthalpy of formation and are promising candidates for new environmentally friendly energetic materials.

关键词： Azofurazan Azide Nitrate ester X-ray Combustion

A general method for one-step synthesis of monofluoroiodane(Ⅲ)reagents using silver difluoride

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Chinese Chemical Letters 2022年第11期33卷 4834-4837页

作者： Jing Ren Meng-Cheng Jia Feng-Huan Du Chi Zhang State Key Laboratory of Elemento-organic chemistry The Research Institute of Elemento-Organic ChemistryCollege of ChemistryNankai UniversityTianjin 300071China

Herein we report a new general method for one-step synthesis of four kinds of fluoroiodane(Ⅲ)reagents by treating the corresponding aryl iodides with silver difluoride(AgF_(2)).This is the first method applicable for the synthesis of all four fluoroiodane(Ⅲ)reagents including p-iodotoluene difluoride(1),fluoro-benziodoxole(2),fluoro-benziodoxolone(3),and fluoro-N-acetylbenziodazole(4).AgF_(2)was firstly employed in the direct oxidative fluorination of iodobenzene and thus has shown its outstanding oxidation and fluorine-transfer ability.The use of AgF_(2)has improved the synthesis of fluoroiodane(Ⅲ)reagents by shortening the reaction steps,avoiding the use of hazardous reagents,and simplifying the experimental operations.It was worth noting that we have developed the first one-step direct synthetic method for 3,while 3 can only be synthesized through Cl→F ligand exchange reaction previously.

关键词： Monofluoroiodane(Ⅲ)reagents Silver difluoride Iodobenzene derivatives One-step synthesis DFT calculations