The Cosolvent-Directed Diels–Alder Reaction in Ionic Liquids
- 28 July 2011
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 115 (36), 10211-10217
- https://doi.org/10.1021/jp205181e
Abstract
The rate constants of a bimolecular Diels–Alder reaction in binary mixtures of ionic liquids prepared in molecular solvents were analyzed to investigate the effect of viscosity of the medium and solvent effect. In this connection, we have carried out the Diels–Alder reaction of anthracene 9-carbinol with N-ethyl maleimide in binary mixtures of pyridinium-based ionic liquids, 1-butyl-pyridinium tetrafluoroborate, 1-butyl-3-pyridinium tetrafluoroborate, and 1-butyl-4-methyl pyridinium tetrafluoroborate in water, methanol, and chloroform at 298.15 K. The rates of reaction decreased, caused by gradually increasing the volume fraction of ionic liquids in solvents for all three ionic liquids. The kinetic results demonstrate a successful application of the pairwise interaction model built upon the concept of enforced hydrophobic hydration. A temperature-dependent study of kinetics of the Diels–Alder reaction was carried out in the binary mixtures of ionic liquids in water and was explained by the entropy–enthalpy compensation effect based upon activation parameters. Kinetics of the Diels–Alder reaction in highly aqueous medium was noted to be entropically driven.Keywords
This publication has 69 references indexed in Scilit:
- Ionic Liquid Electrolyte for Lithium Metal Batteries: Physical, Electrochemical, and Interfacial Studies of N-Methyl-N-butylmorpholinium Bis(fluorosulfonyl)imideThe Journal of Physical Chemistry C, 2010
- Understanding Ionic Liquids at the Molecular Level: Facts, Problems, and ControversiesAngewandte Chemie, 2008
- Diels–Alder Reactions Are Faster in Water than in Ionic Liquids at Room TemperatureAngewandte Chemie, 2006
- Converting exo-Selective Diels−Alder Reaction to endo-Selective in Chloroloaluminate Ionic LiquidsThe Journal of Organic Chemistry, 2004
- A Two-State Model of Hydrophobic Hydration That Produces Compensating Enthalpy and Entropy ChangesJournal of the American Chemical Society, 1996
- Hydrophobic, Highly Conductive Ambient-Temperature Molten SaltsInorganic Chemistry, 1996
- Diels-Alder reactions in aqueous solutions. Enforced hydrophobic interactions between diene and dienophileJournal of the American Chemical Society, 1991
- Quantitative analysis of solvent effects in highly aqueous media. Application of the SWAG procedures and a critical appraisal of the additivity principleJournal of the American Chemical Society, 1990
- Mechanistic Aspects of Diels‐Alder Reactions: A Critical SurveyAngewandte Chemie, 1980
- Notiz über den Lösungsmitteleinfluß auf die Dimerisationsgeschwindigkeit des CyclopentadiensEuropean Journal of Inorganic Chemistry, 1968