Computer-aided molecular design of solvents for accelerated reaction kinetics
| Autor: | Amparo Galindo, Peter R. Haycock, Eirini Siougkrou, Heiko Struebing, Alan Armstrong, Panagiotis G. Karamertzanis, Claire S. Adjiman, Zara Ganase, Patrick M. Piccione |
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| Jazyk: | angličtina |
| Rok vydání: | 2013 |
| Předmět: |
Chemistry
General Chemical Engineering Kinetics General Chemistry Solvent Chemical kinetics Structure-Activity Relationship Reaction rate constant Models Chemical Organic reaction Computational chemistry Solvents Nucleophilic substitution Computer-Aided Design Molecule Organic chemistry Computer Simulation Solvent effects |
| Popis: | Solvents can significantly alter the rates and selectivity of liquid-phase organic reactions, often hindering the development of new synthetic routes or, if chosen wisely, facilitating routes by improving rates and selectivities. To address this challenge, a systematic methodology is proposed that quickly identifies improved reaction solvents by combining quantum mechanical computations of the reaction rate constant in a few solvents with a computer-aided molecular design (CAMD) procedure. The approach allows the identification of a high-performance solvent within a very large set of possible molecules. The validity of our CAMD approach is demonstrated through application to a classical nucleophilic substitution reaction for the study of solvent effects, the Menschutkin reaction. The results were validated successfully by in situ kinetic experiments. A space of 1,341 solvents was explored in silico, but required quantum-mechanical calculations of the rate constant in only nine solvents, and uncovered a solvent that increases the rate constant by 40%. |
| Databáze: | OpenAIRE |
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