Electronic and steric effects in the SNAr substitution reactions of substituted anilines with 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether in acetonitrile
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Rate measurements are reported for the reactions of 12 ring-substituted anilines with 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether (1) in acetonitrile. Formation of the products, the correspondingly substituted 2,4,6- trinitrodiphenylamines, occurs without the observation of intermediates in detectable amounts by both base-catalysed and uncatalysed pathways and Hammett value were determined for these processes. The results show that although substituents at the 3- or 4-positions of the anilines have only small steric effects, alkyl substituents at the 2-position may result in considerable reductions in reactivity. These effects are more pronounced for the base-catalysed pathway and in 2,6-dimethylaniline the uncatalysed pathway takes all the reaction flux. In the case of the 2-fluoro substituent the electronic effect, strong inductive electron withdrawal, is dominant over steric effects.
Research Subject Categories::NATURAL SCIENCES::Chemistry::Physical chemistry::Kinetics , Research Subject Categories::NATURAL SCIENCES::Chemistry::Organic chemistry::Physical organic chemistry
Crampton, M. R., Emokpae, T. A., & Isanbor, C. (2006). Electronic and steric effects in the SNAr substitution reactions of substituted anilines with 2, 4‐dinitrophenyl 2, 4, 6‐trinitrophenyl ether in acetonitrile. Journal of physical organic chemistry, 19(1), 75-80.