52532-59-9Relevant academic research and scientific papers
Reaction of 4-chloro-3,5-dinitrobenzotrifluoride with aniline derivatives. Substituent effects
Al-Howsaway, Hamida O. M.,Fathalla, Magda F.,El-Bardan, Ali A.,Hamed, Ezzat A.
, p. 509 - 512 (2007)
N-(2,6-Dinitro-4-trifluoromethylphenyl)aniline derivatives were prepared by anilino-dechlorination of 4-chloro-3, 5-dinitrobenzotrifluoride. IR, UV and 1H NMR studies suggested an intramolecular hydrogen bond between the amino hydrogen and one o-nitro group. An addition-elimination mechanism was suggested based on the second-order kinetics and the dependence of rates on the nature and the position of the substituent in the aniline ring, as well as the high negative values of p (-3.14, -3.16, -3.01). Such values indicate a positive charge on the aniline nitrogen in the transition state and that the rate is affected by the polar effect of the substituent. The β value (0.85 at 30°C) indicates an appreciable degree of bond formation in the transition state.
Solvent and substituent effects on the reaction of 2- and 4-chloro-3,5-dinitrobenzotrifluorides with substituted anilines
Asghar, Basim H.M.,Fathalla, Magda F.,Hamed, Ezzat A.
supporting information; experimental part, p. 777 - 786 (2010/07/02)
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°C. This reaction is of second order, except 2-chloro-3,5-dinitrobenzotrifluoride in toluene shows third order. The kA values are found to be dependent on the substituent in aniline and give good Hammett correlations. The obtained ρ values are -4.07 and -4.62, for the reaction of anilines with 2-chloro-3,5- dinitrobenzotrifluoride in methanol and acetonitrile, respectively. The ρ 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 on the external base such as DABCO suggests a proton transfer controlling step.
