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DFT STUDIES OF STRUCTURAL PARAMETERS, VIBRATIONAL FREQUENCIES AND NMR SPECTRA OF 3-(1H-BENZO[D]IMIDAZOL-1-YL)-N'-(TOSYLOXY)PROPANIMIDAMIDE 3-(1h -苯并[d]咪唑-1-基)- n′-(tosyloxy)咪唑酰胺结构参数、振动频率和核磁共振谱的DFT研究
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.46
E. Yergaliyeva, L. Kayukova, A. Vologzhanina, G. Baitursynova, V. Vazhev
Amidoxime derivatives have practically valuable biological properties. We have previously obtained new spiropyrazolinium compounds by arylsulfo-chlorination of β-aminopropioamidoximes, but in case of β-(benzimidazol-1-yl)pro-pioamidoxime we have obtained O-substitution product – 3-(1H-benzo[d]imidazol-1-yl)-N'-(tosyloxy)pro-panimidamide. The aim of the work is predicting of structural parameters (bond lengths, bond angles), vibrational frequencies and NMR spectra of 3-(1H-benzo-[d]imidazol-1-yl)-N'-(tosyloxy)propanimidamide. The calculations were performed using Gaussian 09 package. Structural parameters and vibrational frequencies was calculated using DFT (B3LYP/B3PW91/WB97XD)/6-31G(d,p). 1H and 13C NMR was predicted using DFT B3LYP/6-31G(d,p)-GIAO in DMSO. All calculated values are in good agreement with experimental data. The calculated bond lengths and bond angles were compared with results of X-ray structural analysis. The best correlation coefficient was 0.981 (calcu-lations with B3LYP level). For bond angles, the best result was obtained with B3LYP level (0.990). For vibrational frequencies correlation coefficients between the calculated and experimental values were 0.997 (B3LYP), 0.996 (B3PW91) and 0.995 (WB97XD). The most accurate method was used for predic-ting NMR spectrum. The correlation coefficients between the experimental and calculated 1H and 13C chemical shifts were 0.949 and 0.999 respectively.
偕胺肟衍生物具有重要的生物学特性。我们以前用芳基磺化氯化法得到了新的螺吡唑啉化合物,但对于β-(苯并咪唑-1-基)原吡唑胺,我们得到了o取代产物- 3-(1h -苯并咪唑-1-基)- n '-(tosyloxy)原吡唑胺。这项工作的目的是预测3-(1h -苯并-[d]咪唑-1-基)- n '-(tosyloxy)丙酰胺的结构参数(键长,键角),振动频率和核磁共振波谱。使用Gaussian 09软件包进行计算。采用DFT (B3LYP/B3PW91/WB97XD)/6-31G(d,p)计算结构参数和振动频率。用DFT B3LYP/6-31G(d,p)-GIAO在DMSO中预测1H和13C核磁共振。计算值与实验数据吻合较好。将计算得到的键长和键角与x射线结构分析结果进行比较。最佳相关系数为0.981(以B3LYP水平计算)。对于键角,以B3LYP水平(0.990)为最佳。振动频率计算值与实验值的相关系数分别为0.997 (B3LYP)、0.996 (B3PW91)和0.995 (WB97XD)。采用最准确的方法预测核磁共振谱。1H和13C化学位移与实验计算值的相关系数分别为0.949和0.999。
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引用次数: 0
INFLUENCE OF THE RATE OF IRON HEXATIANOFERRATE ON ITS SORPTION ABILITY IN RELATION TO SILVER, INDIUM AND GALLIUM CATIONS 六铁铁的速率对银、铟、镓阳离子吸附能力的影响
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.45
А.А. Agatayeva, U. Jussipbekov, R. Chernyakova, R. Kaiynbayeva, N. Kozhabekova, А.М. Nabiyeva
The processing of phosphorites into elemental phosphorus is accom-panied by the formation of waste - cotrile "milk", in which indium, gallium, and silver are present. This waste can be considered as a cheap raw material for the production of rare and precious metals. In the scientific literature there are data on the sorption capacity of hexacyano-ferrates of iron, which has a crystal lattice with a channel diameter from 3.0 to 3.5Å. Investigation of the sorption process in the model system "Fe4[Fe(CN)6]3·10H2O - Ag+- In3+- Ga3+ - H2O" depending on the norm of iron hexacyanoferrate (sorbent). The initial concentration of silver, indium and gallium ions and their residual content in solutions were determined using the atomic absorption spectrophotometer "PerkinElmer Analyst 400" (USA). The microstructure of the initial iron hexacyanoferrate and iron hexacyano-ferrate, after sorption, was studied on the CarlZeissFESEM and JEOL brand "JXA-8230" (Japan). With a ratio to T:W equal to 1.75-2.5:100, the degree of sorption of Ag+ with iron hexacyanoferrate is 99.5 and 99.8 %. The highest degree of sorption (96.75%) of In3+ ions can be obtained with a sorbent weighing 3 g per 100 g of solution at 60oC. A high degree of sorption of Ga3+ cations is achieved at low (0.5:100 wt. h.) and high (3:100 wt. h.) consumption of iron hexacyanoferrate. It was revealed that iron hexacyanoferrate exhibits sorption properties simultaneously with respect to mono- and trivalent metals, and the basic laws of their sorption were established.
在将磷矿石加工成单质磷的过程中,会产生废料——含有铟、镓和银的芦苇“奶”。这种废物可以被认为是生产稀有和贵重金属的廉价原料。在科学文献中有关于六价高铁酸盐对铁的吸附能力的数据,其晶格的通道直径从3.0到3.5Å。研究了“Fe4[Fe(CN)6]3·10H2O - Ag+- In3+- Ga3+ - H2O”模型体系对六重氰化铁(吸附剂)的吸附过程。用原子吸收分光光度计“PerkinElmer Analyst 400”(美国)测定溶液中银、铟和镓离子的初始浓度及其残留量。在CarlZeissFESEM和JEOL牌“JXA-8230”(日本)上研究了吸附后初始六氰高铁酸铁和六氰高铁酸铁的微观结构。在与T:W的比值为1.75 ~ 2.5:100时,六氰高铁对Ag+的吸附度分别为99.5%和99.8%。在60℃条件下,吸附剂质量为3 g / 100 g,吸附剂对In3+离子的吸附性最高,达到96.75%。在低(0.5:100 wt. h)和高(3:100 wt. h)的六氰高铁消耗下,Ga3+阳离子的高度吸附得到了实现。结果表明,六氰高铁酸铁对一价和三价金属同时具有吸附特性,并建立了其吸附的基本规律。
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引用次数: 0
STUDY OF THE PROCESS OF OXIDATIVE DESULFURIZATION OF DIESEL FUEL IN THE PRESENCE OF CO-CATALYSTS 助催化剂作用下柴油氧化脱硫过程的研究
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.51
D. Muktaly, Z. Myltykbaeva, M. Smaiyl
Continuous growth in consumption of oil in the world, as well as ever-increasing quality requirements stimulate the search for new scientific and technological solutions to directionally affect the characteristics of petroleum products, including their chemical composition. The advantages of oxidative desulfurization before hydrotreating are the absence of the need to use hydrogen, as well as small capital and energy costs, since the method does not require high temperatures and pressures. The purpose of this work was to study the oxidation process of diesel fuel and to search for the optimal mode of oxidative desulfurization of diesel fuel in the presence of transition metals salts with the addition of mineral acids. The object of the study is a straight-run diesel fraction of the Pavlodar Petrochemical Plant with boiling temperatures of 180-350°C. The oxidation process was carried out with hydrogen peroxide in the presence of salts of the transition metals molybdenum, vanadium and tungsten. The article defined the basic physico-chemical characteristics of straight-run and desulfurized diesel fractions. The optimal catalyst (Na2MoO4) was selected at a molar ratio of metal to sulfur of 1:100 for the oxidation process of straight-run diesel fractions. As a result of oxidative desulfurization of diesel fuel in the presence of sodium molybdenum perox complexes, the total sulfur content decreased by 42.9%, and with the addition of sulfuric acid by 56.5%. An increase in the cetane index from 56.3 to 58.6 was revealed in the presence of sodium molybdate with the addition of sulfuric acid.
世界上石油消费的持续增长,以及不断提高的质量要求,促使人们寻求新的科学和技术解决方案,以定向地影响石油产品的特性,包括其化学成分。在加氢处理之前进行氧化脱硫的优点是不需要使用氢气,并且由于该方法不需要高温和高压,因此资金和能源成本小。研究了在过渡金属盐存在下,添加无机酸对柴油氧化脱硫的影响,探索了柴油氧化脱硫的最佳方式。该研究的对象是Pavlodar石化厂的直馏柴油馏分,沸点为180-350°C。在过渡金属钼、钒、钨盐的存在下,用双氧水进行了氧化过程。介绍了直馏馏分和脱硫馏分的基本理化特性。在金属硫摩尔比为1:100的条件下,选择了最优催化剂Na2MoO4用于直馏柴油馏分的氧化反应。在过氧化物钼钠配合物的存在下对柴油进行氧化脱硫,总硫含量降低42.9%,加入硫酸后总硫含量降低56.5%。结果表明,在钼酸钠的存在下,随着硫酸的加入,十六烷指数由56.3提高到58.6。
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引用次数: 0
DIVARENT EQUILIBRIUM IN MULTI-COMPONENT SYSTEMS 多组分系统中的微分平衡
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.49
L. Soliev, M. Jumaev
The structure of the phase complex of the six-component reciprocal system Na, K, Mg, Ca || SO4, Cl-H2O at 500C in the region of crystallization of anhydrite (CaSO4) was studied by the translation method, and variants of the formation of divariant fields during the transition of the system from the five-component to the six-component state were shown
用平移法研究了硬石膏结晶区(CaSO4)中Na、K、Mg、Ca || SO4、Cl-H2O六组分互易体系在500℃时的相配合物结构,揭示了该体系由五组分向六组分转变过程中异变场形成的变化
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引用次数: 0
STUDY OF BIOLOGICAL ACTIVITY OF RACEMIC AND OPTICALLY ACTIVE ESTERS OF NAPHTHENIC AND FATTY ACIDS BASED ON UNSATURATED OXYESTERS 基于不饱和氧酯的环烷基和脂肪酸外消旋和旋光性酯的生物活性研究
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.48
A. Bagirli
Petrochemical products based on petroleum naphthenic acids have special properties. Esters of naphthenic acids possess practically valuable organic compounds. The aim of this work is the development of effective methods for the preparation of aromatic esters based on naphthenic and individual fatty acids which is a very promising direction in the medicine practice. The synthesis of unsaturated racemic and chiral oxyethers was carried out on the basis of the interaction of chloromethylpropargyl (allyl) esters with carbonyl compounds with the participation of metallic zinc. Also, to study the biological activity, racemic and optically active esters were synthesized based on naphthenic acids and unsaturated racemic and chiral oxyesters. As test cultures used: gram-positive (Staphylo-coccus aureus-Staphylococcus aureus), gram-negative (Pseudomonas aeruginosa – Pseu-domonas aeruginosa, Escherichia coli) bacteria, as well as yeast-like fungi of the genus Candida - Candida albicans. Analysis of the biological activity of the synthesized compounds showed that optically active bicyclo [2.2.1] hept-5-ene-2-methylol monoesters have higher antimicrobial and antifungal activity compared to their racemic analogs and drugs used in medicine.
以石油环烷酸为原料的石化产品具有特殊的性能。环烷酸酯具有实际有价值的有机化合物。本工作的目的是开发以环烷基和单个脂肪酸为基础的芳香族酯的有效制备方法,这在医学实践中是一个很有前途的方向。在金属锌的参与下,氯甲基丙炔(烯丙基)酯与羰基化合物相互作用合成了不饱和外消旋氧醚和手性氧醚。此外,为了研究其生物活性,以环烷酸和不饱和外消旋和手性氧酯为基础合成了外消旋和旋光性酯。作为试验培养物:革兰氏阳性(金黄色葡萄球菌-金黄色葡萄球菌),革兰氏阴性(铜绿假单胞菌-铜绿假单胞菌,大肠杆菌)细菌,以及念珠菌属的酵母样真菌-白色念珠菌。合成化合物的生物活性分析表明,光学活性双环[2.2.1]庚-5-烯-2-甲基单酯与它们的外消旋类似物和医学上使用的药物相比,具有更高的抗菌和抗真菌活性。
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引用次数: 0
CYCLODEXTRIN INCLUSION COMPLEXES OF PHARMACEUTICALLY ACTIVE DERIVATIVES OF THE CYTISINE ALKALOID AND THEIR HEMORHEOLOGICAL ACTIVITY 环糊精包合物中具有药用活性的胱氨酸生物碱衍生物及其血液流变学活性
Pub Date : 2021-12-15 DOI: 10.51580/2021-1/2710-1185.50
G.K. Mukusheva, A.R. Zhasymbekova, Z. Satpaeva, Е.V. Minayeva, Z. Nurmaganbetov, S. T. Shulgau, О. Nurkenov, Т. Seilkhanov
The alkaloid cytisine is of great importance for modern pharmacological studies. This alkaloid can be used as a component of the supramolecular system with cyclic oligosaccharides, namely β-cyclodextrins, which have a truncated cone-shaped molecule with internal protons Н3 and Н5 and external ones Н2 and Н4. The aim of the work is to obtain inclusion complexes of pharmaceutically active derivatives of the alkaloid cytisine. The inclusion complexes of cytisine alkaloid derivatives with β-CD and 2-HP-β-CD were obtained by the coprecipitation method. Thermogravimetric, differential thermal, and differential scanning calorimetric analyzes were performed. It was shown that inclusion complexes of substrate with cyclodextrin cavity of receptors were formed. The greatest change in the chemical shifts of protons during the formation of supra-molecular complexes occurs with the internal protons H-3 and H-5 of the cyclodextrin cavity. All calculated values are in good agreement with experimental data. The prepa-ration of supramolecular complexes has been proven using a variety of physicochemical methods of analysis. According to DSC data, the process of complexes destruction in the temperature range of 30-610°C was studied in comparison with the data of the initial cyclodextrin. The hemorheological effects of the investigated samples were studied in vitro. Among four samples studied, two samples showed the ability to reduce blood viscosity in vitro in the blood hyperviscosity model.
生物碱胱氨酸在现代药理学研究中具有重要意义。该生物碱可作为环寡糖超分子体系的组成部分,即β-环糊精,其分子呈截锥状,内部质子Н3和Н5,外部质子Н2和Н4。本工作的目的是获得生物碱的药用活性衍生物的包合物。用共沉淀法得到了胞氨酸生物碱衍生物与β-CD和2-HP-β-CD的包合物。进行了热重、差热和差扫描量热分析。结果表明,底物与环糊精形成包合物,形成受体腔。在超分子配合物形成过程中,质子的化学位移变化最大的是环糊精腔内的H-3和H-5质子。计算值与实验数据吻合较好。超分子复合物的制备已经通过多种物理化学分析方法得到了证实。根据DSC数据,与初始环糊精的数据进行对比,研究了配合物在30 ~ 610℃温度范围内的破坏过程。研究了所研究样品的体外血液流变学效应。在研究的四个样品中,两个样品在体外血液高粘度模型中显示出降低血液粘度的能力。
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引用次数: 0
PLANT SUBSTANCES AS POTENTIAL SOURCE OF ORIGINAL ANTI-VIRUS AGENTS 植物物质是原始抗病毒药物的潜在来源
Pub Date : 2021-09-30 DOI: 10.51580/2021-1/2710-1185.41
S. Adekenov, Karaganda Kazakhstan Production Holding “Phytochemistry”
This article summarizes the literature data and the results of our own studies on the search for antiviral compounds based on terpenoids, flavonoids, alkaloids. New bimolecular and ketoamide derivatives based on sesquiterpene γ-lactones arglabin, grossheimin and α-santonin were synthesized in quantitative yields up to 80%. The molecular docking method was used to study the “structure-activity” relationship of natural compounds and their derivatives in relation to SARS-Cov-2. The results obtained in silico demonstrated that sesquiterpene γ-lactones and their derivatives inhibit the SARS-Cov-2 spike protein and proteases, as well as the angiotensin-converting enzyme 2. The identified molecules can be considered as candidates for the development of new drugs with antiviral activity on their basis.
本文综述了萜类化合物、黄酮类化合物、生物碱类化合物的研究进展及相关文献资料。以倍半萜类γ-内酯精氨酸、毛豆素和α-三冬氨酸为原料合成了新的双分子衍生物和酮酰胺衍生物,产率高达80%。采用分子对接方法研究天然化合物及其衍生物与SARS-Cov-2的“构效”关系。结果表明,倍半萜γ-内酯及其衍生物对SARS-Cov-2刺突蛋白和蛋白酶以及血管紧张素转换酶2具有抑制作用。所鉴定的分子可作为候选分子,在其基础上开发具有抗病毒活性的新药。
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引用次数: 1
MODIFIED WITH VARIOUS ADDITIVES ARYLALYCLIC COPOLYIMIDES AND COMPOSITE FILMS BASED ON THEIR BASIS 用各种添加剂改性芳烃类共聚物和基于它们的复合薄膜
Pub Date : 2021-09-30 DOI: 10.51580/2021-1/2710-1185.36
М.B. Umerzakova, R. Sarieva, V. Kravtsova
lopment of arylalicyclic copolyimides based on alicyclic dianhydride, aromatic dianhydrides of benzophenone- and diphenyloxidetetracarboxylic acids with 4,4'-diaminodiphenyl oxide at various ratios of alicyclic and aromatic dianhydrides, as well as various compositions based on these copolymers with low- or other high-molecular compounds that enhance the characteristics of the polymer matrix. Composite films were formed from solutions of the obtained polymer mixtures, and their properties were studied. It was noted that at optimal ratio of components, the films have improved thermal and strength properties, etc., exceeding the analogous properties of the initial arylalicyclic copolymer, while the elasticity has acceptable values for such material. The best characteristics had the composite films formed from a ternary composition of copo-lyimide-polyethylene glycol-alkylated montmorillonite. Metal-containing composite films, along with higher thermal stability compared to unmodified copolyimide, were resistant to aggressive reagents, lower values of specific volume and surface resistance, higher viscosity values, and different colors depending on the nature of the salt. By introducing a silicon-containing compound into the copolyimide solution, the new polymer systems have been obtained, and the porous films could be formed.
开发以脂环二酐为基础的芳基脂环共聚亚胺,以不同比例的脂环二酐和芳基二苯酮和二苯氧基四羧酸为基础的芳香二酐,以及以4,4'-二氨基二苯基氧化物为基础的各种组合物,这些共聚物与低分子或其他高分子化合物结合,增强了聚合物基体的特性。将得到的聚合物混合物溶液形成复合膜,并对其性能进行了研究。在最佳组分配比下,薄膜的热性能和强度等性能得到改善,超过了初始芳烯环共聚物的类似性能,而弹性具有可接受的值。以共聚酰亚胺-聚乙二醇-烷基化蒙脱土三元组成的复合膜性能最好。与未改性的共酰亚胺相比,含金属的复合膜具有更高的热稳定性,耐腐蚀性试剂,更低的比容和表面电阻,更高的粘度值,以及根据盐的性质不同的颜色。通过在共亚胺溶液中引入含硅化合物,得到了新的聚合物体系,并形成了多孔膜。
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引用次数: 0
INFLUENCE OF THE NATURE OF THE MODIFIER ON THE SORPTION PROPERTIES OF SHANKANAI ZEOLITE 改性剂性质对山卡奈沸石吸附性能的影响
Pub Date : 2021-09-30 DOI: 10.51580/2021-1/2710-1185.37
R. Kaiynbayeva, N.N. Kojabekova, G. Sultanbayeva, А.А. Аgatayeva, R. Chernyakova, U. Jussipbekov
Sorbents modified with hydrochloric acid and chitosan based on the Shankanai bridge formation zeolite were obtained, and the effect of drying temperature on the sorption properties of sorbents was studied. It was found that 25 °C is the optimal temperature for obtaining acid-modified zeolite. A chitosan-modified sorbent with good sorption characteristics can be obtained at 25 °C with cation-exchange (COE 68.05 mg-eq/g) and 70°C with anion-exchange (SEC 70.16 mg-eq/g) properties. Physicochemical analysis of modified zeolites showed an increase in the size of voids and channels on the surface of acid-modified zeolite, and when modified with chitosan, the latter is crosslinked with the surface of natural zeolite.
以山卡内桥型分子筛为基础,制备了盐酸和壳聚糖改性的吸附剂,并研究了干燥温度对吸附剂吸附性能的影响。结果表明,25℃是制备酸改性沸石的最佳温度。壳聚糖改性吸附剂在25℃的阳离子交换性能(COE为68.05 mg-eq/g)和70℃的阴离子交换性能(SEC为70.16 mg-eq/g)下具有良好的吸附特性。对改性沸石的理化分析表明,酸改性沸石表面的孔洞和孔道尺寸增大,壳聚糖改性后,后者与天然沸石表面发生交联。
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引用次数: 0
SYNTHESIS OF 1,2,3-TRIAZOLO-QUINOLIZIDINES BASED ON THE QUINOLIZIDINE ALKALOID LUPININE 以喹啉吡啶类生物碱lupinine为原料合成1,2,3-三唑喹啉吡啶类化合物
Pub Date : 2021-09-30 DOI: 10.51580/2021-1/2710-1185.43
Z. Nurmaganbetov, O.A. Hurkenov, S. Fazylov, G.K. Mukusheva, A. Gazaliyev, Z. Muldakhmetov
The modification of the quinolysin alkaloid lupinine was carried out with the intro-duction of 1,2,3-triazolyl substituents for the hydroxymethylene group in the C-1 position of the quinolysin backbone. The reaction of lupinine with methanesulfochloride in the presence of triethylamine smoothly led to lupinine methanesulfonate, whose further reaction with sodium azide in DMFA led to lupinilazide. 1,3-Dipolar [4+2]-cycloaddition of the resulting azide to alkynes produced more stable 1,2,3-triazole compounds. The interaction of lupinilazide with 2-ethinylpyridine and with alcohols containing a terminal acetylene group (propargyl alcohol, 2-methylbut-3-in -2-ol or hex-5-in -1-ol) proceeded smoothly in the DMFA medium. The reactions were carried out in the presence of an aqueous solution of CuSO4 and sodium ascorbate in DMFA and allowed the corresponding 4-substituted (1S,9aR)-1H-1,2,3-triazol-1-yl to be synthesized with good yields)methyl)octahydro-1H-quinolysins. The results of studying the structural features of synthesized compounds by 1H - and 13C - NMR spectroscopy, as well as data from the two-dimensional COSY (1H-1H) and HMQC (1H-13C) spectra are presented. The values of chemical shifts, multiplicity and integral intensity of 1H and 13C signals in one-dimensional NMR spectra are determined. In the spectra of all synthesized new quinolizi-dinotriazoles, there is a peak of the fragmentary C10H17N ion (150-151 cu), corresponding to the cleavage of the molecule by the C-10 atom of the quinolizidine backbone.
采用1,2,3-三唑基取代喹啉菌素主链C-1位置的羟基取代基,对喹啉菌素生物碱羽氨酸进行了改性。在三乙胺存在下,羽衣嘧啶与甲磺酸盐反应顺利,得到羽衣嘧啶甲磺酸盐,再与叠氮化钠在DMFA中反应得到羽衣嘧啶叠氮化钠。1,3-偶极[4+2]-叠氮化物与炔烃的环加成生成了更稳定的1,2,3-三唑化合物。在DMFA培养基中,lupinilazide与2-乙基吡啶和末端含有乙炔基团的醇(丙炔醇、2-甲基-3-in -2-ol或己-5-in -1-ol)的相互作用顺利进行。该反应在CuSO4和抗坏血酸钠水溶液存在的DMFA中进行,并允许以良好的收率合成相应的4-取代(1S,9aR)- 1h -1,2,3-三唑-1-基)甲基八氢- 1h -喹啉菌素。本文给出了合成化合物的1H- NMR和13C - NMR的结构特征研究结果,以及二维COSY (1H-1H)和HMQC (1H-13C)光谱的数据。确定了一维核磁共振谱中1H和13C信号的化学位移、多重度和积分强度的值。在所有合成的新喹诺齐二硝三唑的光谱中,都有一个C10H17N离子(150 ~ 151 cu)的片段峰,对应于喹诺齐啶主链的C-10原子对分子的裂解。
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引用次数: 1
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Chemical Journal of Kazakhstan
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