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Solvent effects on kinetics of the reaction between 2‐chloro‐3,5‐dinitropyridine and aniline in aqueous and alcoholic solutions of [bmim]BF 4
Author(s) -
HarifiMood Ali Reza,
HabibiYangjeh Aziz,
Gholami Mohammad Reza
Publication year - 2007
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20282
Subject(s) - chemistry , aniline , reaction rate constant , ionic liquid , hydrogen bond , methanol , solvent , reaction rate , aqueous solution , nucleophile , medicinal chemistry , mole fraction , reactivity (psychology) , solvation , ethanol , kinetics , organic chemistry , molecule , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
Rate constants, k A , 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]BF 4 ) 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]BF 4 . In these solutions, rate constants of the reaction decrease with the mole fraction of the ionic liquid. Single‐parameter correlations of log k A versus normalized polarity parameter (E N T ), 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 k A versus E N Tand β also α and β gave reasonable results (e.g., in solutions of water with [bmim]BF 4 , the correlation coefficients are 0.994 and 0.996, respectively). The proposed dual‐parameter models demonstrate that the reaction rate constant increases with E N T , 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. Int J Chem Kinet 39: 681–687, 2007