Nikola Petrović, Graham R. Cumming, Christopher A. Hone, María José Nieves-Remacha, Pablo García-Losada, Óscar de Frutos, C. Oliver Kappe and David Cantillo*,
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引用次数: 0
摘要
我们开发了一个实验设计模型,用于优化在旋转圆筒电极反应器中对吡唑进行脱羧 N- 烷基化反应的电化学方案。电化学反应需要加入分子筛作为添加剂,以确保没有湿气并防止潜在的电极腐蚀问题。事实证明,旋转圆筒电极反应器是将这一涉及固体颗粒悬浮液的转化过程放大到多克级的理想平台。反应模型与实验数据的拟合效果极佳,让我们深入了解了这种反应器设计所独有的重要电解参数(如电极旋转速度)对反应转化率和选择性的影响。此外,实验设计还为这一复杂的多变量反应系统提供了最佳电解参数,在循环流动模式下,600 mL 容积的反应实现了底物的完全转化和优异的选择性,目标 N- 烷基化产物的分离产率达到 94%。
Design of Experiments-Based Optimization of an Electrochemical Decarboxylative Alkylation Using a Spinning Cylinder Electrode Reactor
A design of experiments model has been developed to optimize an electrochemical protocol for the decarboxylative N-alkylation of pyrazole in a spinning cylinder electrode reactor. The electrochemical reaction requires the incorporation of molecular sieves as an additive to ensure the absence of moisture and prevent potential electrode corrosion issues. The spinning cylinder electrode reactor proved to be an ideal platform to scale up this transformation, involving a suspension of solid particles, to multigram scales. The reaction model, which showed an excellent fitting with the experimental data, provided insights into the effect of important electrolysis parameters unique to this reactor design, such as the electrode spinning speed, on the reaction conversion and selectivity. Furthermore, the design of experiments also supplied optimal electrolysis parameters for this complex multivariable reaction system, resulting in full conversion of the substrate and excellent selectivity for a 600 mL volume reaction in recirculation flow mode, with a 94% isolated yield for the target N-alkylated product.
期刊介绍:
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools,process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.