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Solvent effects on aromatic nucleophilic substitution reactions. Part 9. Special kinetic synergistic behavior in binary solvent mixtures

✍ Scribed by P. M. E. Mancini; A. Terenzani; C. Adam; L. R. Vottero

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
122 KB
Volume
12
Category
Article
ISSN
0894-3230

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✦ Synopsis

The kinetics of the reactions of 1-fluoro-2,4-dinitrobenzene with morpholine and piperidine were studied at 25 °C in several binary solvent mixtures of the polar aprotic hydrogen bond acceptor solvent chloroform or dichloromethane type, which, in some cases, exhibit synergism for the E T (30) solvent polarity parameter. In each case, the kinetic response model was analyzed as a function both of the amine concentration and of the solvent mixture composition. The kinetic data show that for some reaction systems under certain experimental conditions, the reactions are faster in binary solvent mixtures than in the corresponding pure solvents, manifesting a special kinetic synergetic behavior. This kinetic effect was attributed to a complex combination of factors related to the variations of the influence of base catalysis with the solvent composition, and to the consequence of specific solvent effects. The kinetic results were related to the E T (30) solvent polarity parameter, analyzing the general validity of the chemical probe for interpreting the solvent effects in the aromatic nucleophilic substitution reactions explored. The applicability of the preferential solvation model allowed the special behavior observed to be attributed to the influence of preferential solvation phenomena.

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