Maltby, K, Sharma, K, Short, M et al. (6 more authors) (2023) Rationalizing and Adapting Water-Accelerated Reactions for Sustainable Flow Organic Processes. ACS Sustainable Chemistry and Engineering, 11 (23). pp. 8675-8684. ISSN 2168-0485
Abstract
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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2023 The Authors. This is an open access article under the terms of the Creative Commons Attribution License (CC-BY 4.0), which permits unrestricted use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | water as a solvent, multiphase flow, on-water reactions |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Organic Chemistry (Leeds) |
Funding Information: | Funder Grant number EPSRC (Engineering and Physical Sciences Research Council) EP/S013768/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 02 Jun 2023 09:41 |
Last Modified: | 19 Jul 2023 15:33 |
Published Version: | https://pubs.acs.org/doi/10.1021/acssuschemeng.3c0... |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acssuschemeng.3c02164 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:199861 |