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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Date
2005-10-28
Authors
Crampton, R.M.
Emokpae, T.A.
Isanbor, C.
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley
Abstract
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.
Description
Keywords
Research Subject Categories::NATURAL SCIENCES::Chemistry::Physical chemistry::Kinetics , Research Subject Categories::NATURAL SCIENCES::Chemistry::Organic chemistry::Physical organic chemistry
Citation
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.