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Continuous dehydration of glycerol to Acrolein based on HPW/TS-COOH catalyzation 基于HPW/TS-COOH催化的甘油连续脱水制丙烯醛
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-02-06 DOI: 10.1007/s41981-023-00260-6
Chen-Xin Su, Jing-Jing Chen, Shao-Yun Wu, Shao-Heng Li, Shou-Quan Zhou, Hui-Dong Zheng, Fu-Weng Zhang

Sustainable synthesis of acrolein, a key chemical intermediate, from biomass-derived glycerol is highly attractive. However, conventional catalysts for the dehydration of glycerol suffer from low acrolein selectivity and high deactivation tendency. Herein, a novel green catalyst (HPW/T0.6 S-COOH) was prepared and employed in the dehydration of glycerol in a continuous flow reactor. The performance of different catalysts and the effects of reaction conditions (reaction temperature, N2 flow rate, and glycerol concentration) were examined. The HPW/T0.6 S-COOH catalyst provides the best glycerol conversion of 96.38% and acrolein selectivity of 92.01%. The NH3-TPD and pyridine-FTIR results indicate that the Brønsted acid site is more susceptible to acrolein, while the weak strength acid site effectively prevents the further reaction of acrolein, providing practical insights for the rational design of efficient and continuous synthesis of acrolein catalysts.

丙烯醛是一种关键的化学中间体,从生物质衍生的甘油中可持续合成丙烯醛是非常有吸引力的。然而,常规的甘油脱水催化剂存在丙烯醛选择性低、失活倾向高的问题。本文制备了一种新型绿色催化剂HPW/T0.6 S-COOH,并将其用于连续流反应器中甘油的脱水。考察了不同催化剂的性能以及不同反应条件(反应温度、N2流量、甘油浓度)对催化剂性能的影响。HPW/T0.6 S-COOH催化剂的甘油转化率为96.38%,丙烯醛选择性为92.01%。NH3-TPD和吡啶- ftir结果表明,Brønsted酸位更容易受到丙烯醛的影响,而弱强度酸位则有效地阻止了丙烯醛的进一步反应,为合理设计高效连续合成丙烯醛催化剂提供了实用的见解。
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引用次数: 0
Multivariate curve resolution for kinetic modeling and scale-up prediction 动力学建模和放大预测的多变量曲线分辨率
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-01-20 DOI: 10.1007/s41981-022-00252-y
Lisa Schulz, Philipp Stähle, Sven Reining, Mathias Sawall, Norbert Kockmann, Thorsten Röder

An imine synthesis was investigated in a nearly isothermal oscillating segmented flow microreactor at different temperatures using non-invasive Raman spectroscopy. Multivariate curve resolution provided a calibration-free approach for obtaining kinetic parameters. The two different multivariate curve resolution approaches, soft and hard modeling, were applied and contrasted, leading to similar results. Taking heat and mass balance into account, the proposed kinetic model was applied for a model-based scale-up prediction. Finally, the reaction was performed in a 0.5 L semi-batch reactor, followed by in-line Raman spectroscopy and off-line gas chromatography analysis. The successful scale-up was demonstrated with a good agreement between measured and predicted concentration profiles.

采用非侵入式拉曼光谱技术研究了不同温度下在近等温振荡分段流微反应器中合成亚胺的过程。多变量曲线分辨率为获得动力学参数提供了一种无需校准的方法。对软建模和硬建模两种不同的多元曲线解析方法进行了应用和对比,得到了相似的结果。考虑到热和质量平衡,将提出的动力学模型应用于基于模型的放大预测。最后,在0.5 L半间歇式反应器中进行反应,然后进行在线拉曼光谱和离线气相色谱分析。成功的放大证明了测量和预测浓度曲线之间的良好一致性。
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引用次数: 0
Continuous flow synthesis of phenyl glucosazone and its conversion to 2H-1,2,3-Triazole building blocks 苯基葡萄糖酮的连续流合成及其转化为2h -1,2,3-三唑基的研究
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-01-16 DOI: 10.1007/s41981-022-00255-9
Maria Molnar, Marcus Baumann

A continuous flow approach for the generation of phenyl glucosazone from glucose and phenyl hydrazine is reported giving the pure target in 53% isolated yield. This thermal process generates the target product as an insoluble material that causes reactor fouling via adhering to the reactor walls. To overcome this issue a segmented flow approach was realised whereby streams of air and the reaction solution were combined in a T-piece and directed through the heated reactor coil. The resulting micro-mixing prevented reactor fouling and blocking and allowed for multi-hour reactions to generate the desired target in high yield. The value of the phenyl glucosazone product was demonstrated via its oxidative cyclisation into 2H-phenyl-1,2,3-triazoles which represent important heterocyclic scaffolds.

本文报道了一种由葡萄糖和苯肼连续流动生成苯代葡萄糖酮的方法,分离产率为53%。这个热过程产生的目标产物是一种不溶性材料,通过附着在反应器壁上导致反应器污染。为了克服这个问题,采用了分段流动的方法,将空气流和反应溶液组合在一个t型管中,并引导通过加热的反应器盘管。由此产生的微混合防止了反应器结垢和堵塞,并允许进行数小时的反应,以高收率产生所需的目标。通过氧化环化生成代表重要杂环支架的2h -苯基-1,2,3-三唑,证明了苯代葡萄糖酮产品的价值。
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引用次数: 1
The applications of organozinc reagents in continuous flow chemistry: Negishi coupling 有机锌试剂在连续流化学中的应用:根岸耦合
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-01-12 DOI: 10.1007/s41981-022-00253-x
Roop Varghese Rubert, Rony Rajan Paul

The design and implementation of flow technique helps organic chemists to resolve numerous challenges that are encountered during various catalytic reactions. Flow technologies, which offer solutions for technical and/or chemical issues, have gained popularity over the last two decades in the field of organic chemistry. The selectivity, efficiency, and safety of the entire process has been accelerated by flow reactors as they improve mass and heat transfer, speeds up the mixing of the reaction, and they offer exact control of the reaction parameters. This review mainly describes the utilization of flow chemistry in reactions involving organiozinc reagent, particularly Negishi coupling. The Negishi coupling of organozinc reagent is a valuable tool for the formation of C-C bond with functional group tolerance and are used extensively in total synthesis. This review also portrays a comparative study of organozinc reagents prepared using different procedures. A study of the effect of different catalysts over the same reaction is also carried out. An overview of different flow techniques that are employed has also been incorporated.

流动技术的设计和实现有助于有机化学家解决在各种催化反应中遇到的许多挑战。流动技术为技术和/或化学问题提供了解决方案,在过去的二十年中在有机化学领域得到了普及。流动反应器改善了质量和传热,加速了反应的混合,并提供了对反应参数的精确控制,从而提高了整个过程的选择性、效率和安全性。本文主要介绍了流动化学在有机锌试剂反应中的应用,特别是根岸偶联反应。有机锌试剂的根岸偶联是形成具有官能团耐受性的C-C键的重要手段,在全合成中得到了广泛的应用。本文还对不同工艺制备的有机锌试剂进行了比较研究。研究了不同催化剂对同一反应的影响。本文还概述了所采用的不同流程技术。
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引用次数: 2
Electrophilic cyclization of reticuline-type alkaloids in flow via o-quinol intermediates 网状型生物碱通过邻喹啉中间体的亲电环化
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-01-12 DOI: 10.1007/s41981-022-00256-8
Bi Bali Judicaël Tra, Abollé Abollé, Killian Lucas, François-Xavier Felpin

Herein, we report the first continuous-flow biomimetic cyclization of reticuline derivatives to aporphine alkaloids via ortho-quinol intermediates. The two-step flow process involves an initial oxidative dearomatization of reticuline derivatives to using hypervalent iodine(III) reagents, followed by a TMSOTf-mediated electrophilic cyclization. The high sensitivity of ortho-quinol compounds is mitigated by the mild experimental conditions and fast reaction rates offered by flow reactors. A preliminary structure–reactivity relationship suggests that both steps of the process are favored with strongly electron-rich substrates, similar to what is observed in nature.

在这里,我们报道了第一个网状衍生物通过邻喹啉中间体连续流动的仿生环化到阿啡生物碱。两步流动过程包括网状衍生物的初始氧化去芳构化,使用高价碘(III)试剂,然后是tmsotf介导的亲电环化。流动反应器提供的温和的实验条件和快速的反应速率减轻了对邻喹啉类化合物的高灵敏度。初步的结构-反应性关系表明,该过程的两个步骤都有利于强富电子衬底,类似于在自然界中观察到的。
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引用次数: 0
Selective monosubstitution on a trichlorosilane with highly reactive organolithium compounds in a microflow reactor 微流反应器中高活性有机锂化合物对三氯硅烷的选择性单取代
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-12-27 DOI: 10.1007/s41981-022-00254-w
Moritz Achternbosch, Lukas Zibula, Annika Schmidt, Waldemar Krieger, Norbert Kockmann, Carsten Strohmann

Organolithium compounds have been used successfully in flow chemistry since the recent past. Most of the studies dealt with the use in halogen-lithium exchanges. So far, however, there has been a lack of use in substitution reactions. The use of flow microreactors makes the highly reactive organolithium compounds more controllable and thus creates new synthetic possibilities.

近年来,有机锂化合物已成功地应用于流动化学。大多数研究涉及卤素-锂交换的应用。然而,到目前为止,在取代反应中还缺乏使用。流动微反应器的使用使高活性有机锂化合物更加可控,从而创造了新的合成可能性。
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引用次数: 0
Reactor performance estimation in microscale flow calorimeter for rapid characterization of exothermic reactions 用于放热反应快速表征的微尺度流动量热计反应器性能评估
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-12-12 DOI: 10.1007/s41981-022-00251-z
Timothy Aljoscha Frede, Nick Nikbin, Norbert Kockmann

Continuous flow calorimeters are a promising tool in process development and safety engineering, especially for flow chemistry applications to characterize the heat release and kinetic parameters of rapid chemical reactions. In this study, the digital accompaniment of an isoperibolic flow calorimeter for characterization of exothermic reactions is presented. To support experimental planning and evaluation, computational fluid dynamic simulations are carried out for single-phase flow in the microreactor. The residence time distribution is obtained and used for estimation of conversion and temperature profiles along the microreactor channel. This leads to an integration of CFD simulations into the calorimeter’s software-guided workflow reducing the experimental effort regarding the determination of thermokinetic data. The approach is tested for a highly exothermic test reaction, which provides further hints for future investigations.

连续流量热计在工艺开发和安全工程中是一种很有前途的工具,特别是在流动化学应用中,用于表征快速化学反应的热释放和动力学参数。在这项研究中,提出了用于表征放热反应的等循环流量量热计的数字伴奏。为了支持实验规划和评估,对微反应器内的单相流动进行了计算流体动力学模拟。得到了停留时间分布,并用于估计微反应器通道的转化和温度分布。这使得CFD模拟集成到量热计的软件指导工作流程中,减少了关于确定热力学数据的实验工作。该方法进行了高放热测试反应的测试,为未来的研究提供了进一步的线索。
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引用次数: 0
TfOH-catalyzed three-component synthesis of Dithiocarbamates from α-Diazoesters under continuous flow conditions 连续流动条件下tfoh催化α-重氮酯合成三组分二硫代氨基甲酸酯
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-12-12 DOI: 10.1007/s41981-022-00249-7
Rui Wang, Hangli He, Qiongjiao Yan, Wei Wang, Haifeng Wang, Fener Chen

The synthesis of dithiocarbamates derivatives is important for their practical utilization as pharmaceuticals and for other purposes. Herein, we demonstrated the TfOH-catalyzed synthesis of dithiocarbamates via three-component reaction of α-diazoesters in good yields under continuous flow conditions. The reaction exhibits a wide substrate scope of diazo compounds and high functional group tolerance. This study provides a safe and mild protocol to form dithiocarbamates that complements TfOH-catalyzed S-H insertion reaction of diazo compounds and continuous flow synthesis strategies.

二硫代氨基甲酸酯衍生物的合成对其作为药物和其他用途的实际应用具有重要意义。在连续流动条件下,通过α-重氮酯的三组分反应,证明了tfoh催化合成二硫代氨基甲酸酯的良好产率。该反应具有广泛的重氮化合物底物范围和高官能团耐受性。本研究提供了一种安全、温和的合成二硫代氨基甲酸酯的方案,补充了tfoh催化的重氮化合物S-H插入反应和连续流合成策略。
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引用次数: 1
Minireview: recent efforts toward upgrading lignin-derived phenols in continuous flow 综述:木质素衍生酚类化合物在连续工艺中的最新进展
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-12-05 DOI: 10.1007/s41981-022-00248-8
Erin E. Brown

Phenols are vital building blocks for manufactured goods, agrochemicals, and medicine. As the demand to circumvent fossil fuels intensifies, so does the need to establish alternate sources of chemical feedstock, with many researchers looking to biomass. Lignin, a complex biopolymer found in plants, represents a relatively untapped renewable source of phenolic compounds. Examples of aromatic compounds derived from lignin include phenol, guaiacol (2-methoxyphenol), and catechol (2-hydroxyphenol). The development of new technologies and chemistry to upgrade or modify these compounds is crucial to realizing the potential of biomass as chemical feedstock. Over the last two decades, continuous flow technology has become an established tool for chemists to expand the capabilities of reaction control and to provide a means to probe novel reactions that might otherwise be difficult to study or accomplish via conventional means. Flow also imparts many advantages, such as superior mixing capabilities for gas/liquid reactions, increased efficiency for photochemical transformations, and improved scalability. This mini review will highlight research efforts reported in the last half-decade (since 2016) toward upgrading lignin-derived phenolic substrates using continuous flow technology. Recent developments focus on reactions requiring oxygenation, oxidation, hydrogenation, and deoxygenation to name a few.

Graphical abstract

酚类物质是制成品、农用化学品和药品的重要组成部分。随着绕开化石燃料的需求日益增加,建立化学原料替代来源的需求也在增加,许多研究人员将目光投向了生物质。木质素是一种复杂的生物聚合物,存在于植物中,是一种相对未开发的可再生酚类化合物。木质素衍生的芳香族化合物包括苯酚、愈创木酚(2-甲氧基酚)和儿茶酚(2-羟基酚)。开发新技术和新化学来升级或修饰这些化合物对于实现生物质作为化学原料的潜力至关重要。在过去的二十年里,连续流技术已经成为化学家扩展反应控制能力的一种成熟工具,并提供了一种方法来探测传统方法难以研究或完成的新反应。流动也带来了许多优势,例如气体/液体反应的卓越混合能力,光化学转化效率的提高以及可扩展性的提高。这篇小型综述将重点介绍过去五年(自2016年以来)使用连续流技术升级木质素衍生的酚醛底物的研究成果。最近的发展集中在需要氧化、氧化、氢化和脱氧的反应上,仅举几例。图形抽象
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引用次数: 0
Mediated formic acid flow fuel cell (MFAFFC) based on biomimetic electrolytes 仿生电解质介导甲酸流动燃料电池(MFAFFC)
IF 2.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-12-02 DOI: 10.1007/s41981-022-00245-x
Katerina Bretosh, Mathieu Beaucamp, Florine Toulotte, Jinyi Yuan, Philippe Hapiot, Maël Penhoat

Water soluble biomimetic models of Riboflavin (B2 vitamin) and Folic acid (B8 vitamin) demonstrated to be good oxidant of formic acid at various pH. Their usage as anolyte mediators in a flow fuel cell to convert formic acid (or formate) into electricity is validated with measured power densities up to 16 mW.cm− 2. These preliminary optimum conditions demonstrated a volumetric energy density of 0.68 Wh.L− 1 when operating at 5 mA.cm− 2 and neutral pH. These new conditions inspired from redox flow batteries processes permit to remove noble metals at both sides of the formate flow fuel cell.

Graphical abstract

核黄素(B2维生素)和叶酸(B8维生素)的水溶性仿生模型被证明在不同ph值下是甲酸的良好氧化剂。它们在流动燃料电池中用作阳极电解质介质,将甲酸(或甲酸)转化为电能,测量功率密度高达16 mW.cm - 2。这些初步的最佳条件表明,体积能量密度为0.68 Wh。工作在5ma时,L−1。这些受氧化还原液流电池工艺启发的新条件允许在甲酸流燃料电池的两侧去除贵金属。图形抽象
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引用次数: 0
期刊
Journal of Flow Chemistry
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