Predicting solvent effects in ionic liquids: E xtension of a nucleophilic aromatic substitution reaction on a benzene to a pyridine

• Published in: Journal of physical organic chemistry 2018-10, Vol.31 (10)
• Main Authors: Hawker, Rebecca R., Haines, Ronald S., Harper, Jason B.
• Format: Article
• Language: English
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.3862

A nucleophilic aromatic substitution reaction involving a halopyridine electrophile was examined in a series of ionic liquid solvents. This reaction was chosen to test the known solvent effects of ionic liquids on this type of reaction mechanism, previously described with a halobenzene electrophile. The effect of varying the proportion of the ionic liquid in solution was determined, and it was shown that the more ionic liquid present in the reaction mixture, the greater the rate constant enhancement. Temperature‐dependent kinetic analyses yielded activation parameters that showed that the rate constant enhancements are controlled by a balance between enthalpic and entropic effects, depending upon the proportion of ionic liquid present. Overall, the rate enhancement is entropically driven, due to organisation of the ionic liquid about the electrophile. These results are consistent with what has been observed previously for the nucleophilic aromatic substitution reaction involving a halobenzene electrophile, demonstrating that the solvent effects observed for ionic liquids are general for this type of reaction mechanism and opening the possibility for extending their use through rational selection for reaction control.