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Impact of gas-solid direct contact on gas-liquid-solid reaction performance in a flow reactor 流动反应器中气固直接接触对气液固反应性能的影响
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-28 DOI: 10.1007/s41981-023-00295-9
Shusaku Asano, Hiroyuki Miyamura, Mizuki Matsushita, Shinji Kudo, Shū Kobayashi, Jun-ichiro Hayashi

Although gas-liquid-solid reactions, such as catalytic hydrogenation, have a long history, a fundamental understanding of the flow behavior and its effect on the reaction is lacking for flow chemistry applications using powder catalysts. This study revealed the distinctive effect of gas-solid direct contact on the surface of a powder catalyst. Direct gas–solid contact accelerates the reaction beyond the theoretical maximum of the batch reaction system, where gaseous species are supplied to the catalyst surface after dissolution into the liquid. The benefit of direct contact is further pronounced in systems with low-solubility gaseous species. Liquid holdup analysis revealed that the micro-concavities of the catalyst support is crucial for sustaining the liquid using capillary forces and supplying the liquid substrate to the catalyst surface even under high gas flow rate conditions. The gas-to-liquid flow rate ratio (G/L) is a decisive factor for direct gas–solid contact, whereas the flow direction, whether upflow or downflow, has no impact on powder catalysts with a size of a few hundred microns.

摘要:虽然催化加氢等气-液-固反应有着悠久的历史,但在粉末催化剂的流动化学应用中,对其流动行为及其对反应的影响还缺乏基本的认识。本研究揭示了粉末催化剂表面气固直接接触的独特效果。气固直接接触使反应加速,超出了间歇反应系统的理论最大值,在间歇反应系统中,气态物质在溶解到液体中后被供应到催化剂表面。在具有低溶解度气体的体系中,直接接触的好处更加明显。液含率分析表明,即使在高气体流速条件下,催化剂支架的微凹孔对于利用毛细力维持液体和向催化剂表面提供液体基质至关重要。气液流量比(G/L)是气固直接接触的决定性因素,而对于几百微米大小的粉末催化剂,流动方向(向上或向下)没有影响。图形抽象
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引用次数: 0
Enhancing N-arylation productivity: the amplified potential of electrophotocatalysis in flow 提高n -芳基化生产力:流动中光电催化的放大潜力
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-28 DOI: 10.1007/s41981-023-00290-0
Jolien De Ketelaere, Thomas S. A. Heugebaert

The recent advances in the area of electrophotocatalysis (EPC) show that it is a highly suitable technique to yield greener and more sustainable organic synthesis. The overall productivity of EPC however is constrained by a multitude of practical limitations, which impose difficulties in effectively harmonizing the photochemical and electrochemical steps, let alone in accelerating both steps simultaneously. In this contribution, we have tackled these limitations by developing a parallel plate flow cell that permits the execution of EPC in continuous flow. By using a transparent electrode, such as fluorine-doped tin oxide (FTO) or indium tin oxide (ITO) coated glass, the interelectrode distance could be reduced while improving photon absorption. By enhancing both the photochemical and electrochemical steps simultaneously, a notable increase in productivity and space–time-yield (a ten-fold and 300-fold improvement, respectively) of the N-arylation of different azoles was observed. In addition, this was achieved in a single-pass process under electrolyte-free conditions.

近年来在光电催化(EPC)领域的进展表明,它是一种非常适合的技术,以产生更绿色和更可持续的有机合成。然而,EPC的总体生产率受到许多实际限制的制约,这些限制在有效协调光化学和电化学步骤方面造成了困难,更不用说同时加速这两个步骤了。在这篇文章中,我们通过开发一种平行板流电池来解决这些限制,该电池允许在连续流动中执行EPC。通过使用透明电极,如掺氟氧化锡(FTO)或氧化铟锡(ITO)涂层玻璃,可以减少电极间距离,同时提高光子吸收。通过同时加强光化学和电化学步骤,观察到不同氮的n-芳基化的生产率和时空产率显著提高(分别提高10倍和300倍)。此外,这是在无电解质条件下的单道过程中实现的。
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引用次数: 0
Investigations on the continuous flow generation of 2,6-dichloro-N-fluoropyridinium tetrafluoroborate using F2 gas F2气连续流动生成2,6-二氯- n -氟吡啶的研究
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-28 DOI: 10.1007/s41981-023-00291-z
Kevin Simon, Desiree Znidar, Gabriel Glotz, Doris Dallinger, C. Oliver Kappe

An explorative study on the continuous flow generation of the N-F reagent 2,6-dichloro-1-fluoro-pyridinium tetrafluoroborate from 2-6-dichloropyridine and 10% F2/N2 and its telescoped downstream electrophilic fluorination reaction with an enamine is reported. The 2-step procedure was performed in a modular lab-scale silicon carbide flow reactor, which safely allowed processing corrosive F2 and precise temperature control. Both reaction sequences turned out to be very fast when carried out in flow at − 10 °C: the N-F generation step could be done within 7.9 s and only 6.6 s were necessary for the fluorination of the enamine.

Graphical abstract

以2-6-二氯吡啶和10% F2/N2为原料,连续流动生成N-F试剂2,6-二氯-1-氟四氟硼酸吡啶,并与一种烯胺进行缩尺下游亲电氟化反应的探索性研究。这两步过程在模块化实验室规模的碳化硅流动反应器中进行,该反应器可以安全地处理腐蚀性F2并精确控制温度。结果表明,在−10°C的流动条件下,这两个反应序列都非常快:N-F的生成步骤可以在7.9 s内完成,而烯胺的氟化只需要6.6 s。图形抽象
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引用次数: 0
Asymmetric electrochemical synthesis in flow 流动中的不对称电化学合成
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-28 DOI: 10.1007/s41981-023-00293-x
Daniele Mazzarella

We are currently experiencing a resurgence in the realm of electrochemical organic synthesis, driven by the transformative potential of conducting redox chemistry under mild conditions through the simple use of electrons, thereby circumventing the use of harmful reductants and oxidants. This renaissance is further bolstered by the fusion of electrochemistry with flow chemistry, which not only grants precise control over reaction parameters but also promotes sustainability and heightened reproducibility. Despite these promising advancements, the application of flow electrochemistry to steer asymmetric processes remains in its nascent stage. This perspective delves into the limited contributions to date, shedding light on critical challenges and presenting prospective solutions that are essential for fully unleashing the untapped potential of this field.

Graphical abstract

目前,我们正在经历电化学有机合成领域的复兴,其驱动力是通过简单使用电子,在温和条件下进行氧化还原化学反应的变革潜力,从而避免使用有害的还原剂和氧化剂。电化学与流动化学的融合进一步推动了这一复兴,它不仅能精确控制反应参数,还能促进可持续性和提高可重复性。尽管取得了这些令人鼓舞的进展,但将流动电化学应用于引导不对称过程的研究仍处于起步阶段。本视角深入探讨了迄今为止的有限贡献,揭示了关键挑战并提出了前瞻性解决方案,这对于充分释放该领域尚未开发的潜力至关重要。
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引用次数: 0
Continuous Flow Generation of Highly Reactive Organometallic Intermediates: A Recent Update 高活性有机金属中间体的连续流动生成:最新进展
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-28 DOI: 10.1007/s41981-023-00292-y
Mauro Spennacchio, Philipp Natho, Michael Andresini, Marco Colella

Reactive organometallic intermediates present a distinct opportunity for the creation of novel carbon-carbon and carbon-heteroatom bonds. Whereas their utility in synthesis is well-established, the thermal sensitivity of these species often imposes the requirement for stringent reaction conditions, including strict control of reaction temperatures, concentrations, and use of additives. Moreover, their strong reactivity can pose challenges in achieving the desired selectivity. Since pioneering works in the 2000s, the advent of flow microreactor technology has revolutionized this field, expanding the possibilities of reactive organometallic intermediates within synthetic chemistry. In this review, we provide an overview of the recent advancements in this dynamic area, focusing on breakthroughs that have emerged within the past four years.

反应性有机金属中间体为创造新的碳-碳和碳-杂原子键提供了独特的机会。虽然它们在合成中的应用是公认的,但这些物质的热敏性通常要求严格的反应条件,包括严格控制反应温度、浓度和添加剂的使用。此外,它们的强反应性对实现期望的选择性提出了挑战。自2000年代的开创性工作以来,流动微反应器技术的出现彻底改变了这一领域,扩大了合成化学中反应性有机金属中间体的可能性。在这篇综述中,我们概述了这个充满活力的领域的最新进展,重点介绍了过去四年中出现的突破。
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引用次数: 0
Nitration process of 2-(2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-1,2,4-triazol-3-one in a microreactor 微反应器中 2-(2,4-二氯苯基)-4-(二氟甲基)-5-甲基-1,2,4-三唑-3-酮的硝化过程
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-09 DOI: 10.1007/s41981-023-00289-7
Jian-yang Cao, Jing Hou, Le-wu Zhan, Bin-dong Li

In a continuous flow microreactor system, a continuous nitration process of 2-(2,4-dichloro-5-nitrophenyl)-4-(difluoromethyl)-5-methyl-1,2,4-triazol-3-one which is the key intermediate for the synthesis of important triazolinone herbicide Sulfentrazone was developed. The effects of molar ratio of mixed acids, molar ratio of nitric acid to substrate, reaction temperature, total flow rate and residence time in the microreactor on nitration reaction were studied. The results showed that when the flow rate of the material was 60 mL/min, the molar ratio of nitrate to sulfur mixed acid was 1:6, the molar ratio of nitric acid to raw material was 1.1:1, the reaction temperature was 60 ℃, and the residence time was 30 s, the product can be obtained in 97% yield. Compared with the results of nitration process using traditional batch reactors, the use of continuous flow microreactors improved reaction efficiency and achieved higher yields. A characterization kinetics study was conducted on this reaction, and the pre-exponential-factor and activation energy for 2-(2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-1,2,4-triazol-3-one nitration were obtained. The activation energy of the reaction is 40.204 kJ/mol. The continuous flow microreactor system greatly increased liquid-liquid two phases mass transfer efficiency, while accurately controlling the reaction temperature and residence time in the reactor.

在连续流微反应器系统中,开发了 2-(2,4-二氯-5-硝基苯基)-4-(二氟甲基)-5-甲基-1,2,4-三唑-3-酮的连续硝化工艺,该工艺是合成重要的三唑酮类除草剂磺草酮的关键中间体。研究了混合酸的摩尔比、硝酸与底物的摩尔比、反应温度、总流量和在微反应器中的停留时间对硝化反应的影响。结果表明,当物料流速为 60 mL/min、硝硫混合酸摩尔比为 1:6、硝酸与原料摩尔比为 1.1:1、反应温度为 60 ℃、停留时间为 30 s 时,产品收率可达 97%。与使用传统间歇反应器进行硝化过程的结果相比,使用连续流微反应器提高了反应效率,并获得了更高的产率。对该反应进行了表征动力学研究,得到了 2-(2,4-二氯苯基)-4-(二氟甲基)-5-甲基-1,2,4-三唑-3-酮硝化反应的预指数和活化能。反应的活化能为 40.204 kJ/mol。连续流微反应器系统大大提高了液液两相的传质效率,同时精确控制了反应器中的反应温度和停留时间。
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引用次数: 0
Leveraging flow chemistry for the synthesis of trisubstituted isoxazoles 利用流动化学合成三取代异噁唑
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-08 DOI: 10.1007/s41981-023-00288-8
Michael Prieschl, Niklas Sulzer, Joerg Sedelmeier, Dainis Kaldre, René Lebl, Kurt Püntener, Stefan Hildbrand, Jason D. Williams, C. Oliver Kappe

The synthesis of trisubstituted isoxazoles generally requires multiple individual chemical steps, making them amenable to improvements in efficiency by telescoping as a multistep flow process. Three steps (oximation, chlorination and cycloaddition) were developed in continuous flow mode, aiming to function as an high-yielding and efficient sequence. We demonstrate this sequence using two aldehyde starting materials of interest: one carbocyclic and one heterocyclic. Between these two substrates, significant differences in solubility and reactivity necessitated modifications to the route. Most notably, the chlorination step could be carried out using either an organic N-Cl source (applicable for the carbocyclic aldehyde) or Cl2 generated on-demand in a flow setup (applicable for the heterocyclic aldehyde). By selecting the most effective method for each substrate, good yields could be achieved over the telescoped sequence.

三取代异噁唑的合成通常需要多个单独的化学步骤,因此可以通过伸缩为一个多步骤流程来提高效率。我们以连续流模式开发了三个步骤(氧化、氯化和环化),旨在实现高产高效的序列。我们使用两种感兴趣的醛类起始材料(一种是碳环,一种是杂环)演示了这一步骤。这两种底物在溶解性和反应性方面存在显著差异,因此有必要对路线进行修改。最值得注意的是,氯化步骤可以使用有机 N-Cl 源(适用于碳环醛)或在流动装置中按需生成的 Cl2(适用于杂环醛)。通过为每种底物选择最有效的方法,可以在伸缩序列中获得良好的产率。
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引用次数: 0
Synthesis of BuNENA in a continuous flow microreactor 在连续流微反应器中合成苯并萘胺
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-07 DOI: 10.1007/s41981-023-00287-9
Zhi-Yuan Jiang, Jing Hou, Le-Wu Zhan, Bin-Dong Li

In order to improve process safety, product purity, and production efficiency in the synthesis of N-n-butyl-N-(2-nitroxy-ethyl)nitramine (BuNENA), a two-stage continuous flow microreactor system was constructed by sequentially connecting the self-designed heart-shaped channel microreactor and the caterpillar microreactor. n-Butylethanolamine was used as the raw material, nitric acid and acetic anhydride were used as the nitrating agents. The results showed that when the flow rate of n-butylethanolamine was 1.00 mL.min− 1, the temperature of the heart-shaped channel microreactor was 10 ℃, the temperature of the caterpillar microreactor was 35 ℃, the molar ratio of ZnCl2 to n-butylethanolamine was 2%, the molar ratio of nitric acid to n-butylethanolamine was 2.4, and the molar ratio of ZnCl2 to n-butylethanolamine was 2.4, the result was best. Under the conditions, the reaction time was shortened to 300 s, the purity of BuNENA was up to 98.1%, and the yield was 87.1%.

为了提高合成N-正丁基-N-(2-硝基-乙基)硝胺(BuNENA)的工艺安全性、产品纯度和生产效率,将自行设计的心形通道微反应器和履带式微反应器依次连接,构建了两级连续流微反应器系统。结果表明,当正丁基乙醇胺的流速为 1.00 mL.min- 1 时,心形通道微反应器的温度为 10 ℃,履带式微反应器的温度为 35 ℃,氯化锌与正丁基乙醇胺的摩尔比为 2%,硝酸与正丁基乙醇胺的摩尔比为 2.4,氯化锌与正丁基乙醇胺的摩尔比为 2.4,结果最佳。在此条件下,反应时间缩短至 300 秒,BuNENA 的纯度高达 98.1%,收率为 87.1%。
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引用次数: 0
Investigating the photochemical reaction of an oxazolone derivative under continuous-flow conditions: from analytical monitoring to implementation in an advanced UVC-LED-driven microreactor 研究连续流条件下一种恶唑酮衍生物的光化学反应:从分析监测到先进的紫外线-LED 驱动微反应器的实施
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-07 DOI: 10.1007/s41981-023-00284-y
Gaëlle Lebrun, Marie Schmitt, Michael Oelgemöller, Marc Vedrenne, Jean-François Blanco, Karine Loubière

This study examined the photochemical transformation of an oxazolone derivative in a continuous microreactor irradiated by a UVC LED array (273 nm). The aim of this study was to transfer the reaction protocol originally developed under batch conditions to continuous flow and to further evaluate the scope of this application. A custom-built UVC-LED panel was combined with a microchip, and this microflow system allowed to work under perfectly controlled operating conditions. NMR and LC-MS were used to identify and quantify the main products obtained during the reaction. From this, an HPLC method was developed for imine separation, allowing for an easy and fast monitoring of the reaction progress. Subsequently, the influence of the operating conditions (residence time, photon flux density, temperature) on the selectivity and conversion was investigated to identify the most favorable conditions for a specific product. Temperature did not affect conversion but had an impact on the reaction’s selectivity. The developed UVC-LED-driven continuous-flow microreactor was found to be very efficient since a quantum photon balance ratio of 0.7 was enough to convert all the reactant, while at the same time achieving the maximal yield of the target product. Exhaustive irradiation did not change the molar ratio of each compound present in the reaction medium, thus excluding follow-up photoreactions of the products. This work opens promising perspectives for boosting flow photochemistry in the UV-C domain.

Graphical abstract

本研究考察了一种恶唑酮衍生物在紫外 LED 阵列(273 纳米)照射的连续微反应器中的光化学转化。本研究的目的是将最初在间歇条件下开发的反应方案转移到连续流动条件下,并进一步评估这一应用的范围。定制的紫外线 LED 面板与微芯片相结合,这种微流系统可以在完全受控的操作条件下工作。使用 NMR 和 LC-MS 对反应过程中获得的主要产物进行鉴定和定量。由此,开发出了一种用于亚胺分离的高效液相色谱法,可以方便快捷地监测反应的进展情况。随后,研究了操作条件(停留时间、光子通量密度、温度)对选择性和转化率的影响,以确定对特定产物最有利的条件。温度对转化率没有影响,但对反应的选择性有影响。研究发现,所开发的紫外-LED 驱动连续流微反应器非常高效,因为 0.7 的量子光子平衡比足以转化所有反应物,同时还能获得目标产物的最大产量。完全辐照不会改变反应介质中每种化合物的摩尔比,从而排除了产物的后续光反应。这项工作为促进 UV-C 领域的流动光化学开辟了前景广阔的前景。
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引用次数: 0
The joint effort of enzyme technology and flow chemistry to bring biocatalytic processes to the next level of sustainability, efficiency and productivity 酶技术和流动化学的共同努力将生物催化工艺的可持续性、效率和生产率提升到新的水平
IF 2 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-07 DOI: 10.1007/s41981-023-00286-w
Silvia Donzella, Martina Letizia Contente

The number of biocatalyzed reactions at industrial level is growing rapidly together with our understanding on how we can maximize the enzyme efficiency, stability and productivity. While biocatalysis is nowadays recognized as a greener way to operate in chemistry, its combination with continuous processes has lately come up as a powerful tool to enhance process selectivity, productivity and sustainability. This perspective aims at describing the recent advances of this technology and future developments leading to smart, efficient and greener strategies for process optimization and large-scale production.

Graphical Abstract

随着我们对如何最大限度地提高酶的效率、稳定性和生产率的认识不断加深,工业级生物催化反应的数量也在迅速增长。如今,生物催化已被公认为一种更环保的化学操作方式,而生物催化与连续工艺的结合也已成为提高工艺选择性、生产率和可持续性的有力工具。本视角旨在介绍这一技术的最新进展和未来发展,从而为工艺优化和大规模生产提供智能、高效和更环保的策略。
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引用次数: 0
期刊
Journal of Flow Chemistry
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