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One pot three component synthesis of 2-amino-4H-chromene derivatives under microwave irradiation using Sr2As2O7 nanocatalyst 微波辐照下Sr2As2O7纳米催化剂一锅三组分合成2-氨基- 4h -铬衍生物
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.20994.1872
L. Kafi‐Ahmadi, S. Khademinia, Rozhin Esmaeili
2-Amino-4H-chromene compounds are belonged to an important heterocyclic groups that have extensive important in organic chemistry and medicine. The compounds have anti-cancer, anti-bacterial, anti-coagulation and anti-tumor properties and have applications to produce dye, make up and hygienic materials. Until know, several methods have been reported for the synthesis of the compounds. Most of them, suffers defects such as poisoning and volatile solvents, low yield, high length reaction time, and no reusability of used catalyst. In the present work, Sr2As2O7 pyrochlore material was used as a catalyst for the synthesis of 2-amino-4H-cromens derivatives using a three component one-pot synthesis method under microwave irradiation. The raw materials were aromatic aldehydes, malononitrile and beta-naphtol. Sr2As2O7 was synthesized by an ultrasonic assisted solvothermal method using H2O and C2H5OH solvents mixtures at the 1:1 volumetric ratio. The materials were characterized by PXRD, FESEM and FTIR techniques. Then, the catalytic performance of the synthesized nanomaterial was used for the synthesis of 2-amino-4H-chromene derivatives. To do the process, the reaction parameters such as reaction time, solvent type and catalyst amount were optimized and the reactions were performed under the conditions. It was found that the optimum conditions were 15 mg catalyst, H2O as solvent and 6-9 min reaction time.
2-氨基- 4h -铬化合物是一类重要的杂环基团,在有机化学和医学上具有广泛的应用价值。该化合物具有抗癌、抗菌、抗凝血和抗肿瘤等特性,可用于生产染料、化妆品和卫生材料。到目前为止,已经报道了几种合成这些化合物的方法。它们大多存在中毒、溶剂挥发、产率低、反应时间长、催化剂不可重复使用等缺陷。本文以Sr2As2O7焦绿盐为催化剂,在微波辐射下采用三组分一锅法合成了2-氨基- 4h -克罗门衍生物。原料为芳香族醛、丙二腈和-萘酚。以水和C2H5OH为溶剂,体积比为1:1,采用超声辅助溶剂热法合成了Sr2As2O7。采用PXRD、FESEM和FTIR技术对材料进行了表征。然后,将合成的纳米材料的催化性能用于合成2-氨基- 4h -铬衍生物。对反应时间、溶剂类型、催化剂用量等参数进行了优化,并在此条件下进行了反应。结果表明,最佳反应条件为催化剂15 mg,水为溶剂,反应时间6 ~ 9 min。
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引用次数: 0
Photocatalytic reduction of nitro aromatic compounds to their corresponding amino aromatic compounds by rGO/ZnFe2O4 under visible light irradiation rGO/ZnFe2O4在可见光下光催化还原硝基芳香族化合物为相应的氨基芳香族化合物
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.21751.1914
Leila Masti, A. Bezaatpour, N. Bozari, Y. Azizian-Kalandaragh
In this research work, the rGO/ZnFe2O4 photocatalyst was prepared by hydrothermal method and characterized and identified using X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FE-SEM), Diffuse Reflectance Spectroscopy (DRS), vibrating-sample magnetometer (VSM), surface area analysis (BET) and Energy-dispersive X-ray spectroscopy (EDAX) techniques. The photocatalyst was used for the reduction of nitroaromatic compounds to their corresponding aromatic amines with hydrazine monohydrate. The catalyst showed the best activity in the reduction of 1,4-dinitrobenzen (%97 conversion in 40 min). The recyclability and reusability of the catalyst was evaluated for four times which showed no significant variation in the conversion of nitrobenzene photoreduction reaction.
本研究采用水热法制备了rGO/ZnFe2O4光催化剂,并利用x射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、场发射扫描电镜(FE-SEM)、漫反射光谱(DRS)、振动样品磁强计(VSM)、表面积分析(BET)和能量色散x射线能谱(EDAX)等技术对rGO/ZnFe2O4光催化剂进行了表征。该光催化剂用于硝基芳香族化合物与一水合肼还原成相应的芳胺。该催化剂对1,4-二硝基苯的还原活性最佳(40 min转化率为97%)。对催化剂的可回收性和可重复使用性进行了4次评价,对硝基苯光还原反应的转化率无显著影响。
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引用次数: 0
Green and three-component synthesis of 2-cyclohexylamino-2-oxo-1-arylethyl/alkyl thiophene-3-carboxylates in aqueous medium 绿色和三组分合成2-环己基氨基-2-氧-1-芳乙基/烷基噻吩-3-羧酸盐
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2020.20958.1869
Sima Mosavi Niaraki, Abbas Azimi Roshan, A. Monfared, Hamze Kiani
From the Passerini three-component reaction between cyclohexyl isocyanide, thiophene-2-carboxylic acid and aryl/alkyl aldehydes, some new compounds of 2-cyclohexylamino-2-oxo-1-arylethyl/alkyl thiophene-3-carboxylates have been synthesized in 30-45 min in yields in the range of 85% to 90%. Reactions were performed in water solvent and room temperature. The structure of the synthesized compounds was characterized using infrared (IR) and nuclear magnetic resonance (NMR). The use of water as a green solvent, the reaction without energy consumption and at room temperature, no use of catalyst, separation without the use of chromatographic techniques, and the high yields of the reaction are the significant advantages of this Passerini reaction. The antibacterial properties of the synthesized compounds were also tested. The results of experiments showed that these compounds exhibit good antibacterial properties.
从环己基异氰化物、噻吩-2-羧酸和芳基/烷基醛的Passerini三组分反应中,在30-45 min内合成了一些新的2-环己基氨基-2-氧基-1-芳基乙基/烷基噻吩-3-羧酸盐化合物,收率在85% ~ 90%之间。反应在水、溶剂和室温下进行。利用红外光谱(IR)和核磁共振(NMR)对所合成化合物的结构进行了表征。采用水作为绿色溶剂,反应无能耗且在室温下进行,不使用催化剂,分离不使用色谱技术,反应收率高是该反应的显著优点。并对合成的化合物进行了抗菌性能测试。实验结果表明,这些化合物具有良好的抗菌性能。
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引用次数: 0
Methane production by CO2 photo-reduction in the presence of TiO2 modified by Nickel and Copper 镍和铜改性TiO2存在下CO2光还原制甲烷研究
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.19404.1776
Reza Nematollahi, A. Larimi, C. Ghotbi, F. Khorasheh, Mohsen Moradi
Carbon dioxide photocatalytic reduction is one of the promising methods used to produce a wide range of renewable hydrocarbon fuels using sunlight in the presence of photocatalysts. In this study, a series of nickel-doped titanium dioxide samples (0.5, 1, and 1.5 wt%) Were synthesized by Sol-gel method. After performing photocatalytic carbon dioxide recovery experiments and finding the optimum percentage of nickel, titanium dioxide sample with 1 wt% nickel (TNi1) showed the highest photocatalytic activity. Then, by impregnation method, 3% by weight of Cu (1, 2 and 3 wt%) was loaded onto the TNi1 structure. Finally, the sample loaded with 1 wt% copper on titanium dioxide doped with 1 wt% Ni (1Cu/TNi1) showed the highest photocatalytic activity and methane production was 12.6 μmol/gcat that was about 4 times higher than the amount of methane produced in the presence of pure TiO2. The synthesized nanophotocatalysts were characterized using X-ray diffraction (XRD) analysis, diffuse reflectance spectroscopy (DRS) analysis and photoluminescence (PL) analysis. Also, their specific surface area was measured by BET method and morphology of the particles was investigated by field emission scanning electron microscopy.
二氧化碳光催化还原是一种很有前途的方法,用于在光催化剂的存在下利用太阳光生产各种可再生碳氢化合物燃料。本研究采用溶胶-凝胶法合成了一系列掺杂镍的二氧化钛样品(质量分数为0.5、1和1.5 wt%)。通过光催化二氧化碳回收实验,找到最佳镍含量,镍含量为1 wt%的二氧化钛样品(TNi1)具有最高的光催化活性。然后,通过浸渍法,将重量为3%的Cu(1、2和3 wt%)加载到TNi1结构上。最后,在掺杂1 wt% Ni (1Cu/TNi1)的二氧化钛上负载1 wt%铜的样品表现出最高的光催化活性,甲烷产量为12.6 μmol/gcat,是纯TiO2存在时甲烷产量的4倍左右。采用x射线衍射(XRD)分析、漫反射光谱(DRS)分析和光致发光(PL)分析对合成的纳米光催化剂进行了表征。用BET法测定了颗粒的比表面积,并用场发射扫描电镜研究了颗粒的形貌。
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引用次数: 2
Extraction of Active Ingredients from Shiraz City Bitter Orange Peel with supercritical carbon dioxide and soxhlet 超临界二氧化碳-索氏法提取设拉子城市苦橘皮有效成分研究
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.20609.1876
A. Zarei, N. Esfandiari
In this study, two methods of soxhlet extraction and supercritical carbon dioxide extraction were used to extract the effective substances in bitter orange peel. In supercritical fluid extraction, the effect of operational parameters such as temperature, pressure, dynamic time and particle size at different levels on extraction efficiency was investigated. To investigate the more accurate effect of the parameters, the design of the experiment was carried out and the response method was used and a model was obtained for the percentage of extraction efficiency by changing the parameters. The extracted materials were compared with two methods. One of the most important extracted materials is ostol and limonene. The amount of ostol in oil extracted by supercritical carbon dioxide is significantly higher than soxhlet method. The best extraction conditions with supercritical carbon dioxide, dynamic time of 80 minutes, temperature of 35 °C, pressure of 157.26 bar and particle size of 0.4099 mm were obtained.
本研究采用索氏提取和超临界二氧化碳提取两种方法提取苦橙皮中的有效物质。在超临界流体萃取中,考察了不同温度、压力、动态时间和不同粒径等操作参数对萃取效率的影响。为了研究参数对提取效率的更准确影响,进行了实验设计,采用响应法,建立了参数变化对提取效率百分比的影响模型。比较了两种方法提取的物质。其中最重要的提取物质是牡醇和柠檬烯。超临界二氧化碳法提取的油中甾醇的含量明显高于索氏法。最佳萃取条件为超临界二氧化碳,萃取时间为80 min,萃取温度为35℃,萃取压力为157.26 bar,萃取粒度为0.4099 mm。
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引用次数: 0
Ultrasonic-assisted degradation of a methylene blue using CuCo2O4 as a heterogeneous Fenton-like catalyst 以CuCo2O4为非均相Fenton-like催化剂,超声辅助降解亚甲基蓝
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.21478.1902
M. Nekoeinia, Samira Vahedi, Farideh Salehriahi
In this study, a copper cobaltite nanostructure was prepared as a non-ferrous heterogeneous Fenton catalyst using a one-step solvothermal method. The prepared nanocatalyst was characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), infrared spectroscopy (FT-IR) and energy-dispersive X-ray spectroscopy (EDS). The prepared CuCo2O4 exhibited outstanding activity for the degradation of methylene blue (MB) in aqueous solutions under ultrasonic irradiations. The degradation efficiency of MB was only 27.4 % in the absence of catalyst, whereas it reached more than 95.0 % in the presence of the CuCo2O4 after 60 min of ultrasonic irradiation. The trapping experiments with two radical scavengers (tert-butanol and chloroform) showed that both hydroxyl and superoxide radicals are generated during the decomposition of H2O2 and played important roles in oxidation of MB. The prepared nanocatalyst demonstrated good catalytic stability over three successive runs, without any remarkable decrease in catalytic activity.
在本研究中,采用一步溶剂热法制备了钴酸铜纳米结构作为非铁非均相Fenton催化剂。采用x射线衍射(XRD)、场发射扫描电镜(FESEM)、红外光谱(FT-IR)和能量色散x射线光谱(EDS)对所制备的纳米催化剂进行了表征。制备的CuCo2O4在超声照射下对水溶液中的亚甲基蓝(MB)具有良好的降解活性。在没有催化剂的情况下,MB的降解效率仅为27.4%,而在CuCo2O4存在的情况下,超声波照射60 min后,MB的降解效率可达95.0%以上。用两种自由基清除剂(叔丁醇和氯仿)进行的捕集实验表明,在H2O2分解过程中产生羟基自由基和超氧自由基,并在MB的氧化过程中发挥重要作用。制备的纳米催化剂在连续三次运行中表现出良好的催化稳定性,催化活性没有明显下降。
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引用次数: 0
Measuring of metanephrine by UV-Vis peak of surface absorption Plasmon resonance of silver nanoparticles by response surface methodology 响应面法测定纳米银表面吸收等离子体共振紫外-可见峰中肾上腺素的含量
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.20465.1850
Ehsan Sotoodeh, D. Almasifar, Jafar Burromandpiroze
A simple and low-cost spectrophotometry method was proposed based on resonance Plasmon peak of silver nanoparticles for measurement of metanephrine(MN) drug. This method was based on reducing property of metanephrine and it was founded that this compound reduces silver ions in presence of polyvidone (PVP) as stabilizer compound. In this condition the formed silver nanoparticles show a localized surface plasmon resonance (LSPR) peak of about 423 nm. The resulted nano-particles were analyzed by transmission electron microscope (TEM) technique and nanoparticles size was estimated to be maximum of 200nm. Furthermore, realized that the absorption of solution depends on concentration of metanephrine and the maximum of absorption was found at 〖AgNO〗_3 concentration of 1.53 mM, NaOH concentration of 4.10 mM, 〖NH〗_3 concentration of 2.51 mM and 1.15 ml of PVP. Also, the proposed method showed a good linear relationship than MN concentration in the range of 2.5-20 µM and limit of detection was obtained as 0.6 µM for metanephrine. Finally, this method was used for measuring epinephrine in real samples and the acceptable results were obtained.
提出了一种基于纳米银共振等离子体峰的分光光度法测定肾上腺素(MN)药物的方法。该方法基于肾上腺素的还原特性,发现该化合物在聚维酮(PVP)作为稳定剂存在下,对银离子具有还原作用。在此条件下形成的银纳米粒子显示出约423 nm的局部表面等离子体共振(LSPR)峰。通过透射电子显微镜(TEM)对所得纳米颗粒进行了分析,估计纳米颗粒的最大尺寸为200nm。此外,还发现溶液的吸收率与肾上腺素的浓度有关,在〖AgNO〗_3浓度为1.53 mM、NaOH浓度为4.10 mM、〖NH〗_3浓度为2.51 mM和PVP浓度为1.15 ml时,溶液的吸收率最大。该方法与MN浓度在2.5 ~ 20µM范围内呈良好的线性关系,对甲氧基肾上腺素的检出限为0.6µM。最后,将该方法用于实际样品中肾上腺素的测定,得到了可接受的结果。
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引用次数: 0
Experimental and theoretical study of hydrolysis for some oxidized urazoles 一些氧化脲唑水解的实验与理论研究
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.20267.1830
Hadi Beiginejad, Shadi Paziresh, Shadpoor Malekpoor
In this work electrochemical oxidation of some urazole derivatives (1–6) was studied both experimentally and theoretically. The results indicate that the urazoles are converted to oxidized forms (1ox-6ox) via two electron process. The produced species (1ox-6ox) are unstable and participate in hydrolysis reaction, and ring cleavage happens after electrochemical process. Depending on the substituent that is connected to the urazol ring, the rates of the hydrolysis are different. Because the charge of reaction site and bond order of C1-N1 bond are effective on the hydrolysis rate, using computational study, the effects of the both parameters on the hydrolysis rate were analyzed. It was found that various substituents by affecting on the both parameters change the hydrolysis rate. After drawing diagrams of charge of reaction site and bond order of C1-N1 bonds versus hydrolysis rate, it was shown that there are significant relationship between these parameters and hydrolysis rate. Finally these results were used to estimation of hydrolysis rate of some other urazoles (7-10) without conducting laboratory research.
本文从实验和理论两方面研究了一些乌拉唑衍生物(1-6)的电化学氧化反应。结果表明,乌拉唑通过双电子过程转化为氧化态(1ox-6ox)。生成的物质(1ox-6ox)不稳定,参与水解反应,电化学过程后发生环解理。根据与脲唑环连接的取代基的不同,水解速率是不同的。由于反应位点的电荷和C1-N1键的键序对水解速率有影响,因此采用计算研究的方法,分析了这两个参数对水解速率的影响。研究发现,不同的取代基通过影响这两个参数来改变水解速率。通过绘制反应位点电荷和C1-N1键的键序与水解率的关系图,可以看出这些参数与水解率之间存在着显著的关系。最后,这些结果用于估计其他一些乌拉唑(7-10)的水解率,而不进行实验室研究。
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引用次数: 0
Electrochemical oxidation of 4-amino phenol in the presence of 2-mercaptobenzimidazoles and synthesis of new organosulfur compounds 2-巯基苯并咪唑存在下4-氨基苯酚的电化学氧化及新有机硫化合物的合成
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2021.19496.1781
A. Amani, S. Torabi
In this research, the electrochemical oxidation of 4-amino phenol (1) was studied by cyclic voltammetry and controlled potential coulometryin in the absence and presence of 2-mercaptobenzimidazole (3a), 2-mercapto-5-methyl benzimidazole (3b) and 2-mercapto-5-metoxy benzimidazole (3c) in aqueous/ethanol (70/30 v/v) mixture.The results revealed that p-quinone(2) derived from oxidation of 4-amino phenol (1) participate in Michaeladdition reactions with 3a-c via EC mechanism. To confirm the proposed mechanism, the electrochemical synthesis of 4-amino phenol (1) was performed in the presence of 2-mercapto benzimidazoles (3a-c), and the obtained products were identified by 1HNMR, FTIR and Mass spectroscopy. In this study, we synthesized a variety of products with good efficiency using controlled potential electrochemical oxidation at a surface of graphite electrode.
本研究采用循环伏安法和控制电位库伦法,研究了2-巯基-5-甲基苯并咪唑(3a)、2-巯基-5-甲基苯并咪唑(3b)和2-巯基-5-甲氧基苯并咪唑(3c)在水/乙醇(70/30 v/v)混合物中不存在和不存在时4-氨基苯酚(1)的电化学氧化。结果表明,4-氨基酚(1)氧化生成的对醌(2)通过EC机制参与了与3a-c的michael加成反应。为了证实上述机理,在2-巯基苯并咪唑(3a-c)存在下进行了4-氨基酚(1)的电化学合成,并通过1HNMR、FTIR和质谱对所得产物进行了鉴定。在本研究中,我们利用可控电位电化学氧化在石墨电极表面合成了多种高效的产物。
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引用次数: 0
Photocatalytic application of a phosphonate-based metal-organic framework for the removal of bisphenol A under natural sunlight 自然光照下磷酸盐基金属有机骨架光催化脱除双酚a的研究
Pub Date : 2021-09-23 DOI: 10.22075/CHEM.2020.20122.1818
A. Farrokhi, Farzaneh Bivareh, Saeideh Dejbakhshpour, A. Z. Moghaddam
Photocatalytic removal of bisphenol A, one of the most widely and emerging pollutants in the aquatic environment, was investigated by advanced oxidation process under natural sunlight. The removal process by a metal-organic framework, synthesized with phosphonic acid ligand, namely STA-12 (Fe) and hydrogen peroxide revealed excellent results. Therefore, the optimal conditions for the degradation of bisphenol A by the photo-Fenton mechanism were studied. The removal process follows the first-order kinetics with respect to the contaminant and a significant synergy was observed in the catalytic system of hydrogen peroxide/sunlight/STA-12 (Fe). The Optimal values for pH, irradiation time, catalyst amount and H2O2 dosage for oxidation of bisphenol A in 30 mg / l aqueous solution were determined to be 5, 90 minutes, 10 mg and 12 μl, respectively. Under these conditions, the best removal efficiency was 79.8%. Also, the mineralization value of organic pollutant was determined to equal 51% by measuring TOC. To determine the most important species that affected the photocatalytic reduction, trapping experiments were carried out, using various kinds of scavengers and the results showed that the hydroxyl radicals (•OH) are the main oxidizing agent in the photocatalytic system and superoxide radical and the holes in the photocatalyst surface are less involved in the process of contaminant degradation. Finally, a probable reaction mechanism has been investigated in detail. In addition, the catalyst has recyclability and stability in the photocatalytic reaction. This study is the first report for application of a phosphonate-based MOF for the removal of an emerging pollutant with a photo-Fenton mechanism and presents a new example of solar-driven advanced oxidation process for the treatment of aquatic sources and environmental protection.
双酚A是水生环境中应用最广泛和新兴的污染物之一,本文研究了在自然光照下采用高级氧化法光催化去除双酚A。采用磷酸配体STA-12 (Fe)和过氧化氢合成的金属有机骨架去除效果良好。为此,研究了光- fenton降解双酚A的最佳条件。在过氧化氢/太阳光/STA-12 (Fe)的催化体系中观察到明显的协同作用,污染物的去除过程遵循一级动力学。在30 mg / l的水溶液中,双酚A氧化的最佳pH值为5 μl,最佳照射时间为90 min,最佳催化剂用量为10 mg,最佳H2O2用量为12 μl。在此条件下,最佳去除率为79.8%。通过测定TOC,确定有机污染物的矿化值为51%。为了确定影响光催化还原的最重要物种,利用各种清除剂进行了捕集实验,结果表明,羟基自由基(•OH)是光催化体系中的主要氧化剂,超氧自由基和光催化剂表面的孔较少参与污染物降解过程。最后,详细探讨了可能的反应机理。此外,该催化剂在光催化反应中具有可回收性和稳定性。本研究首次报道了磷酸盐基MOF在光- fenton机制下去除新兴污染物的应用,为太阳能驱动的高级氧化工艺在水源处理和环境保护方面提供了新的范例。
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引用次数: 0
期刊
Applied Chemistry
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