Abstract
The solvent effect on a nucleophilic substitution reaction of 2- and 4-chloro-3,5-dinitrobenzotrifluoride with substituted anilines was studied in methanol, acetonitrile, and toluene at 25 degrees C. This reaction is of second order, except 2-chloro-3,5-dinitrobenzotrifluoride in toluene shows third order. The k(A) values are found to be dependent on the substituent in aniline and give good Hammett correlations. The obtained rho values are -4.07 and -4.62, for the reaction of anilines with 2-chloro-3,5-dinitrobenzotrifluoride in methanol and acetonitrile, respectively. The rho values for the reaction of the anilines with 4-chloro-3,5-dinitrobenzotrifluoride are -3.38, -4.11, and -4.34 in methanol, acetonitrile, and toluene, respectively. The reaction of the former compound with anilines in toluene shows a second order in aniline. The dependence of the reaction oil the external base such as DABCO suggests a proton transfer controlling step. (C) 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 777-786, 2009