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Electronic and steric effects in the SNAr substitution reactions of substituted anilines with 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether in acetonitrile

Crampton, Michael R.; Emokpae, Thomas A.; Isanbor, Chukwuemeka

Authors

Michael R. Crampton

Thomas A. Emokpae

Chukwuemeka Isanbor



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.

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. https://doi.org/10.1002/poc.997

Journal Article Type Article
Acceptance Date Sep 7, 2005
Online Publication Date Oct 28, 2005
Publication Date Jan 1, 2006
Deposit Date Apr 26, 2007
Journal Journal of Physical Organic Chemistry
Print ISSN 0894-3230
Electronic ISSN 1099-1395
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 19
Issue 1
Pages 75-80
DOI https://doi.org/10.1002/poc.997
Keywords SNAr substitution reactions, Anilines, 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether, Electronic effects, Steric effects.