Rationalizing and Adapting Water-Accelerated Reactions for Sustainable Flow Organic Processes.
Rationalizing and Adapting Water-Accelerated Reactions for Sustainable Flow Organic Processes.
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DOI：
10.1021/acssuschemeng.3c02164
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发表时间：
2023-06-12
影响因子：
8.4
通讯作者：
Nguyen, Bao N.
中科院分区：
文献类型：
--
作者：
Maltby, Katarzyna A.;Sharma, Krishna;Short, Marc A. S.;Farooque, Sannia;Hamill, Rosalie;Blacker, A. John;Kapur, Nikil;Willans, Charlotte E.;Nguyen, Bao N.
其中至少一种有机反应物不溶于水的水加速反应是一类重要的有机反应，对化学制造工艺的可持续性具有潜在的关键影响。然而，由于这些过程的复杂和多变的物理和化学性质，对控制加速效应的因素的机械理解是有限的。本文建立了一个计算已知水加速反应速率加速度的理论框架，给出了与实验数据相关的ΔG_∞变化的计算估计。深入研究了N-甲基靛红和硝基甲烷之间的亨利反应，使用我们的框架导致合理化的反应动力学，它缺乏对混合的依赖，动力学同位素效应，以及不同的盐效应与NaCl和Na 2SO 4。基于这些发现，多相流过程，其中包括连续相分离和循环的水相的开发，并证明其上级绿色指标（PMI反应= 4和STY = 0.64公斤L-1小时-1）。这些发现为进一步在计算机上发现和开发水加速反应以实现可持续制造奠定了重要基础。一个理论和实践的框架，预测，合理化，并适应水加速反应到整体可持续的流动过程已被证明。
Water-accelerated reactions, wherein at least one organic reactant is not soluble in water, are an important class of organic reactions, with a potentially pivotal impact on sustainability of chemical manufacturing processes. However, mechanistic understanding of the factors controlling the acceleration effect has been limited, due to the complex and varied physical and chemical nature of these processes. In this study, a theoretical framework has been established to calculate the rate acceleration of known water-accelerated reactions, giving computational estimations of the change to ΔG‡ which correlate with experimental data. In-depth study of a Henry reaction between N-methylisatin and nitromethane using our framework led to rationalization of the reaction kinetics, its lack of dependence on mixing, kinetic isotope effect, and different salt effects with NaCl and Na2SO4. Based on these findings, a multiphase flow process which includes continuous phase separation and recycling of the aqueous phase was developed, and its superior green metrics (PMI-reaction = 4 and STY = 0.64 kg L–1 h–1) were demonstrated. These findings form the essential basis for further in silico discovery and development of water-accelerated reactions for sustainable manufacturing. A theoretical and practical framework for predicting, rationalizing, and adapting water-accelerated reactions into holistically sustainable flow processes has been demonstrated.
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