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Visible light-promoted metal-free aerobic photooxidation of xanthenes, thioxanthenes and dihydroacridines in deep eutectic solvents 可见光促进深共晶溶剂中杂蒽、硫杂蒽和二氢吖啶的无金属有氧光氧化
Pub Date : 2023-11-14 DOI: 10.1016/j.tgchem.2023.100030
Sarah-Jayne Burlingham, Alejandro Torregrosa-Chinillach, Diego A. Alonso, Rafael Chinchilla

Benzylic systems such as 9H-xanthenes, 9H-thioxanthenes and 9,10-dihydroacridines can be easily oxidized to the corresponding xanthones, thioxanthones or acridones, respectively, in deep eutectic solvents by a visible blue light-promoted photooxidation procedure carried out using ambient air as oxidant in the presence of riboflavin tetraacetate as a metal-free photocatalyst. The obtained yields are high or almost quantitative, and the reaction media can be recovered and reused. The environmental friendliness of the protocol is demonstrated based on several green metrics.

9h -杂蒽、9h -硫杂蒽和9,10-二氢吖啶酮等苯系化合物可在深共晶溶剂中,通过可见光促进的光氧化过程,在四乙酸核黄素作为无金属光催化剂的存在下,以环境空气为氧化剂,分别氧化为相应的杂蒽酮、硫杂蒽酮或吖啶酮。所得收率高或几乎定量,反应介质可回收再利用。基于几个绿色指标证明了协议的环境友好性。
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引用次数: 0
Role of organic solvent and influence of oxidant in the oxidation of linalool catalyzed by molybdenum and vanadium complexes 有机溶剂在钼钒配合物催化芳樟醇氧化中的作用及氧化剂的影响
Pub Date : 2023-10-01 DOI: 10.1016/j.tgchem.2023.100029
Ali Al Hadi Haidar , Dominique Agustin

The coordination complexes [MoO2(SAP)]2 [Mo] and [VO(SAP)]2O [V] (SAP = salicylideneamino-phenolato) were tested as pre-catalysts for oxidation of a biomass-issued substrate, linalool (L). The reaction was studied using different oxidants, TBHP (in water or in decane) or H2O2 (in water with/without acetonitrile). Efficient linalool (L) conversions were obtained with selectivity towards two selected products, 2-(5-methyl-5- vinyltetrahydro-furan-2-yl propan-2-ol) (1) and 2,2,6- trimethyl-6-vinyltetrahydro-2H-pyran-3-ol (2) depending on pre-catalysts and oxidant. Green metrics have been calculated and showed the role of organic solvent for the process.

配合物[MoO2(SAP)]2[Mo]和[VO(SAP)]2O[V](SAP=亚水杨基氨基苯酚)被测试为用于氧化生物质释放的底物芳樟醇(L)的预催化剂。使用不同的氧化剂,TBHP(在水中或癸烷中)或H2O2(在含有/不含有乙腈的水中)研究反应。根据预催化剂和氧化剂,对两种选择的产物2-(5-甲基-5-乙烯基四氢-呋喃-2-基丙-2-醇)(1)和2,2,6-三甲基-6-乙烯基四四氢-2H-吡喃-3-醇(2)具有选择性地获得了有效的芳樟醇(L)转化。已经计算了绿色指标,并显示了有机溶剂在该过程中的作用。
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引用次数: 0
Photoredox/HAT dual-catalyzed carboxylation of benzyl chlorides with CO2 using thiophenolate and formate as reductants 以噻吩酸酯和甲酸盐为还原剂,光氧化还原/HAT双催化氯化苄与CO2的羧化反应
Pub Date : 2023-09-07 DOI: 10.1016/j.tgchem.2023.100028
Zhengning Fan , Yaping Yi , Chanjuan Xi

Carboxylation of benzyl chlorides with CO2 has been developed with photoredox/HAT dual-catalysis. The reaction could be conducted at room temperature with blue LED light source. Potassium formate (HCO2K) is used as a green reductant and a catalytic amount of sodium thiophenolate (PhSNa) is applied as the HAT reagent. Strongly reductive carbon dioxide radical anion (CO2‧–) is produced to promote the cleavage of C–Cl bond.

在光氧化还原/HAT双催化下,开发了苄基氯与CO2的羧化反应。反应可以在室温下用蓝色LED光源进行。甲酸钾(HCO2K)用作绿色还原剂,催化量的硫代酚酸钠(PhSNa)用作HAT试剂。产生强还原性的二氧化碳自由基阴离子(CO2‧–)以促进C–Cl键的断裂。
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引用次数: 0
A short review: Chemo-catalytic CO2 insertion in amine and amino alcohols to produce linear and cyclic carbamates 化学催化CO2插入胺和氨基醇制备线性和环状氨基甲酸酯的研究进展
Pub Date : 2023-09-04 DOI: 10.1016/j.tgchem.2023.100024
Sharda Kondawar , Chetana Patil , Sadhana Raylu , Chandrashekhar Rode

The adverse effect of carbon dioxide occurred in past decade on environment, led researchers to use CO2 as a C1 building block for the synthesis of various commodity chemicals. Most of the drug molecules and polymers have back bone of carbon chain which provides great opportunity to researchers, to make use of CO2 as an abundant and renewable source of carbon. Chemo-catalytic synthesis of industrially important cyclic and open chain carbamate using amino alcohol/alcohol and amine in presence of CO2 as carbonylating agent has got much more attention in recent years. This review focuses on the literature survey from 1986 to 2022 on carbamate synthesis and provides clear idea about prerequisite active sites in catalyst for the activation of CO2 which is a major challenge. The details of mechanism proposed for the chemo-catalytic pathway has been discussed in detail in order to understand and design the novel and efficient catalyst system in near future in this demanding research field.

过去十年中,二氧化碳对环境产生了不利影响,导致研究人员将二氧化碳作为合成各种商品化学品的C1组成部分。大多数药物分子和聚合物都有碳链的主链,这为研究人员利用二氧化碳作为丰富可再生的碳源提供了巨大的机会。近年来,以氨基醇/醇和胺为催化剂,在CO2存在下化学催化合成工业上重要的环状和开链氨基甲酸酯受到了越来越多的关注。这篇综述的重点是1986年至2022年关于氨基甲酸酯合成的文献调查,并对CO2活化催化剂中的先决条件活性位点提供了明确的认识,这是一个重大挑战。为了在不久的将来理解和设计这一要求很高的研究领域中的新型高效催化剂体系,已经详细讨论了化学催化途径的机理细节。
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引用次数: 0
Continuous flow enantioselective processes catalysed by cinchona alkaloid derivatives 金鸡纳生物碱衍生物催化的连续流动对映选择性反应
Pub Date : 2023-08-28 DOI: 10.1016/j.tgchem.2023.100025
Elisabete P. Carreiro , Anthony J. Burke , Gesine J. Hermann , Hans-Jürgen Federsel

Without a doubt, asymmetric catalysis has been significantly enriched by the introduction of cinchona alkaloid derivatives. Moreover, such methods have been further enabled when used in conjunction with continuous flow systems.

Besides being used in flow chemistry as organocatalysts, they also have been used as ligands or modifiers of metal catalysts. This has generally been accomplished via their immobilization on heterogeneous supports and incorporation into catalysis-enabling reactors or similar systems. In this minireview we look at the impact that cinchona-based catalysts and analogues have had on the field of continuous flow-chemistry during the last two decades or so.

毫无疑问,金鸡纳生物碱衍生物的引入大大丰富了不对称催化作用。此外,当与连续流系统结合使用时,这种方法已被进一步启用。除了在流动化学中用作有机催化剂外,它们还被用作金属催化剂的配体或改性剂。这通常是通过将它们固定在多相载体上并结合到催化反应器或类似系统中来实现的。在这篇小型综述中,我们观察了金鸡纳基催化剂和类似物在过去二十年左右对连续流化学领域的影响。
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引用次数: 0
Tandem CuI – Zinc dust as a sustainable catalyst for the preparation of propargylamine derivatives via an A3 coupling reaction, under neat conditions 串联CuI -锌粉作为可持续催化剂,在整洁条件下通过A3偶联反应制备丙胺衍生物
Pub Date : 2023-08-19 DOI: 10.1016/j.tgchem.2023.100027
Mercy E. Agbo, Hannah N. Heinz, Jasmine B. Mather, Jean Fotie

The cooperative activity of two proximal metal ions is well-known to exhibit highly efficient and synergistic catalytic activities in living organisms. Owing to this knowledge, tandem Cu–Zn systems have been widely used to catalyze a diversity of chemical transformations. This report describes the use of CuI and zinc dust as a sustainable tandem catalyst for the preparation of propargylamines via a three-component coupling reaction under neat conditions. This reaction proceeds at low temperature, and produces good yields with a number of aliphatic and aromatic aldehydes. The reactivity of a number of amines and alkynes has also been explored under these reaction conditions, resulting in 33 fully characterized compounds prepared in the process. Among the ketones tested during this study, only cyclohexanone was able to produce the expected product in a decent yield. The catalytic system reported here represents one of the sustainable approaches to the preparation of propargylamines, as it involves the use of naturally abundant metals as a tandem catalyst, at a low temperature and under neat conditions.

众所周知,两种近端金属离子的协同活性在生物体中表现出高效和协同的催化活性。由于这些知识,串联Cu–Zn系统已被广泛用于催化多种化学转化。本报告描述了CuI和锌粉作为一种可持续的串联催化剂在纯条件下通过三组分偶联反应制备炔丙基胺的用途。该反应在低温下进行,并与许多脂肪族和芳香族醛产生良好的产率。在这些反应条件下,还探索了许多胺和炔烃的反应性,得到了33种完全表征的化合物。在这项研究中测试的酮中,只有环己酮能够以可观的产量生产出预期的产物。本文报道的催化体系代表了制备炔丙基胺的可持续方法之一,因为它涉及在低温和纯条件下使用天然丰富的金属作为串联催化剂。
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引用次数: 0
A green deprotection strategy: Removing acid-labile protecting groups using lemon juice/ethanol as the solvent 绿色去保护策略:用柠檬汁/乙醇作为溶剂去除酸不稳定的保护基团
Pub Date : 2023-08-18 DOI: 10.1016/j.tgchem.2023.100026
Weiding Wang, Yinzhe Chen, Xiaoheng Li, Qian Zhang

Lemon juice has been studied and reported as an efficient catalyst or green medium in organic synthesis. The present digest paper shows the successful and efficient Removal of multiple acid-labile protecting groups using crude lemon juice for the first time. Several drops of lemon juice can rapidly convert some simple liquid acetals to carbonyl compounds. Also, when mixed with ethanol, lemon juice effectively removes cyclic acetals and other protection groups on primary or secondary alcohols. In addition, for the selective Removal of acetonide on diacetone-d-glucose and its derivatives, the yield can reach more than 85%. Lemon juice, combined with ethanol as a solvent, can avoid using hazardous organic or inorganic acids to remove acid-labile protecting groups while being environmentally friendly.

柠檬汁已被研究并报道为有机合成中的有效催化剂或绿色介质。本文首次用柠檬汁成功有效地去除了多种酸不稳定保护基。几滴柠檬汁可以快速将一些简单的液体缩醛转化为羰基化合物。此外,当与乙醇混合时,柠檬汁可以有效地去除伯醇或仲醇上的环状缩醛和其他保护基团。此外,对于二丙酮-d-葡萄糖及其衍生物选择性去除丙酮,产率可达85%以上。柠檬汁与乙醇作为溶剂相结合,可以避免使用危险的有机酸或无机酸来去除酸不稳定的保护基团,同时对环境友好。
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引用次数: 0
Heterogeneous flow chemistry through bamboo-based microfluidic reactors 竹材基微流控反应器的非均相流动化学研究
Pub Date : 2023-08-12 DOI: 10.1016/j.tgchem.2023.100022
Omar Ginoble Pandoli

The rapid development of flow chemistry and its related microfluid technology has accelerated the innovation in material science and the research into alternative, environmentally, and cost-effective microfabrication procedures. This article reviews the latest advances in bamboo-based microfluidic devices, highlighting the heterogeneous catalysis in flow mode through the three-dimensional (3D) structures of the plant's vascular bundles. Different strategies for immobilizing catalysts (metal and enzymes) and the design of the lignocellulosic-based flow reactor are presented.

流动化学及其相关微流体技术的快速发展加速了材料科学的创新和对替代性、环保性和成本效益高的微制造程序的研究。本文综述了基于竹子的微流体装置的最新进展,重点介绍了通过植物维管束的三维(3D)结构在流动模式下进行的多相催化。介绍了固定催化剂(金属和酶)的不同策略以及基于木质纤维素的流动反应器的设计。
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引用次数: 0
Development and characterization of a continuous ultrasound emulsification and nano-emulsion polymerization process 连续超声乳化与纳米乳液聚合工艺的开发与表征
Pub Date : 2023-08-12 DOI: 10.1016/j.tgchem.2023.100023
Jonas Loncke , Arne Vancleef , Wim Dermaut , Leen Braeken , Leen C.J. Thomassen

Typically, nano-emulsions are prepared in batch high-speed homogenization or ultrasound processes and polymerized afterwards in batch reactors. However, fully continuous processes have the potential to decrease production costs and energy consumption compared to batch processes. This research thus focuses on implementing ultrasound into a fully continuous emulsification and nano-emulsion polymerization process to obtain latex nano-particles from butylmethacrylate and ethylene glycol dimethacrylate. The goal of this research is to produce nano-emulsions and nano-particles with the smallest obtainable size and polydispersity in a fully continuous two-stage process. In the first stage or emulsification stage, parameters like flowrate, residence time and acoustic power are varied to influence and determine the optimal energy density. In second stage or reaction stage, residence time and reaction temperature are studied to obtain particles of monodisperse sizes. Samples produced in both stages are analysed with Dynamic Light Scattering to measure the average size and polydispersity (PdI) of the emulsion droplets and particles. Emulsification results indicate that droplet size and PdI decreases at increasing energy densities (J/ml) until 60 J/ml after which a constant droplet size of 150 nm and PdI of 0.230 are reached. Furthermore, a particle size of 50 nm and PdI of 0.080 were achieved in both batch and continuous polymerization reactors after 5 min at 85 °C. By implementing the most optimal process parameters, small emulsion droplets and particles were obtained more energy efficient in a shorter emulsification and reaction time compared to literature ultrasound assisted nano-emulsion polymerization processes.

通常,纳米乳液是在分批高速均化或超声过程中制备的,然后在分批反应器中聚合。然而,与分批工艺相比,完全连续工艺有可能降低生产成本和能耗。因此,本研究的重点是将超声波应用于完全连续的乳化和纳米乳液聚合过程中,以甲基丙烯酸丁酯和二甲基丙烯酸乙二醇为原料制备乳胶纳米粒子。这项研究的目标是在完全连续的两阶段过程中生产具有最小可获得尺寸和多分散性的纳米乳液和纳米粒子。在第一阶段或乳化阶段,流量、停留时间和声功率等参数变化,以影响和确定最佳能量密度。在第二阶段或反应阶段,研究停留时间和反应温度以获得单分散尺寸的颗粒。用动态光散射分析两个阶段中产生的样品,以测量乳液液滴和颗粒的平均尺寸和多分散性(PdI)。乳化结果表明,液滴尺寸和PdI随着能量密度(J/ml)的增加而减小,直到60J/ml,之后达到150nm的恒定液滴尺寸以及0.230的PdI。此外,在85°C下5分钟后,在分批和连续聚合反应器中均获得了50 nm的颗粒尺寸和0.080的PdI。通过实施最优化的工艺参数,与文献中超声辅助的纳米乳液聚合工艺相比,在更短的乳化和反应时间内获得了更节能的小乳液液滴和颗粒。
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引用次数: 0
Green and sustainable bio-synthesis of gold nanoparticles using Aspergillus Trinidadensis VM ST01: Heterogeneous catalyst for nitro reduction in water Trinidadensis曲霉VM ST01绿色可持续生物合成纳米金:水中硝基还原的多相催化剂
Pub Date : 2023-08-02 DOI: 10.1016/j.tgchem.2023.100021
Amar G. Deshmukh , Vyoma Mistry , Abhishek Sharma , Paresh N. Patel

In this study, a gold nanoparticles (GNPs) have been successfully fabricated by the bio reduction route using soil extract Aspergillus trinidadensis (VM ST01’ OL587588) fungi as a reducing and capping agent without any solvent interference. The GNPs were grown and stabilized by a two-step one-pot method, without any influence of chemical reactants. Characteristics of prepared GNPs were investigated using various microscopic and spectroscopic techniques. GNPs were roughly spherical in shape. Water dispersion study of GNPs has shown a stable dispersion in a broad range of 2–12 pH. The stirring and precursor salt concentration has influenced the kinetics involved in the fabrication process. Stoichiometric data has shown 3.5 × 1020 gold atoms per gram of biomass with diameters of around 35 nm, as determined with High-Resolution Transmission Electron Microscopy (HR-TEM). Zeta potential and Powder X-Ray Diffraction (P-XRD) studies have elucidated the crystalline nature of GNPs. Presence of participating functional groups were examined with Fourier Transform Infra-Red Spectroscopy (FT-IR). Synthesized GNPs were analyzed for surface morphology by Scanning Electron Microscope (SEM). The thermal stability of the lyophilized GNPs sample and capping of the particle were evaluated with Thermo-Gravimetric Analysis (TGA) and had a residual mass of 25% at 306 °C. The Aspergillus trinidadensis capped GNPs have been demonstrated as an efficient heterogeneous catalyst (AtGNHC) for the reduction of 4-Nitrophenol as a model substrate in water. An isolated yield (>95%) of the reduced product in 4 h has shown the effectiveness of the prepared catalyst.

在本研究中,使用土壤提取物三硝基曲霉(VM ST01’OL587588)真菌作为还原剂和封端剂,在没有任何溶剂干扰的情况下,通过生物还原途径成功制备了金纳米粒子(GNPs)。GNP通过两步一锅法生长和稳定,不受任何化学反应物的影响。使用各种显微镜和光谱技术研究了所制备的GNP的特性。GNP大致呈球形。GNP的水分散体研究表明,GNP在2–12 pH的宽范围内具有稳定的分散性。搅拌和前体盐浓度影响了制造过程中涉及的动力学。化学计量数据显示,用高分辨率透射电子显微镜(HR-TEM)测定,每克直径约为35nm的生物质有3.5×1020个金原子。Zeta电位和粉末X射线衍射(P-XRD)研究阐明了GNPs的结晶性质。用傅立叶变换红外光谱(FT-IR)检测参与官能团的存在。通过扫描电子显微镜(SEM)分析合成的GNP的表面形态。用热重分析(TGA)评估冻干GNP样品的热稳定性和颗粒的封端,并在306°C下具有25%的残留质量。三硝基曲霉封端的GNP已被证明是一种有效的多相催化剂(AtGNHC),用于在水中还原4-硝基苯酚作为模型底物。4小时内还原产物的分离产率(>95%)显示了所制备的催化剂的有效性。
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引用次数: 1
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Tetrahedron Green Chem
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