Solvent effects on kinetics of the reaction between 2-chloro-3,5- dinitropyridine and aniline in aqueous and alcoholic solutions of [bmim]BF 4

Harifi Mood, A ; Sharif University of Technology | 2007

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  1. Type of Document: Article
  2. DOI: 10.1002/kin.20282
  3. Publisher: 2007
  4. Abstract:
  5. Rate constants, kA. for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 1-(1-butyl)-3-methylimidazolium terafluoroborate ([bmim]BF4) mixed with water, methanol, and ethanol at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: water > methanol > ethanol > [bmim]BF4. In these solutions, rate constants of the reaction decrease with the mole fraction of the ionic liquid. Single-parameter correlations of log kA versus normalized polarity parameter (ETN), hydrogen bond acceptor basicity (β), hydrogen bond donor acidity (α), and dipolarity/polarizability (π*) do not give acceptable results in all solutions. Dual-parameter correlations of log kA versus E TN and β also α and β gave reasonable results (e.g., in solutions of water with [bmim]BF4, the correlation coefficients are 0.994 and 0.996, respectively). The proposed dual-parameter models demonstrate that the reaction rate constant increases with E TN, β, and α. The increase in the rate constant is attributed to hydrogen-bonding interactions (donor and acceptor) of the media with an activated complex of the reaction that has the zwitterionic character. © 2007 Wiley Periodicals, Inc
  6. Keywords:
  7. Aniline ; Hydrogen bonds ; Ionic liquids ; Methanol ; Rate constants ; Correlation coefficients ; Dual-parameter models ; Mole fraction ; Reaction kinetics
  8. Source: International Journal of Chemical Kinetics ; Volume 39, Issue 12 , December , 2007 , Pages 681-687 ; 05388066 (ISSN)
  9. URL: https://onlinelibrary.wiley.com/doi/10.1002/kin.20282