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The aminolysis and hydrolysis of N-(4,6-diphenoxy-1,3,5-triazin-2-yl) substituted pyridinium salts: Concerted displacement mechanism

Cullum, Neil R., Rettura, Donatella, Whitmore, James M.J., Williams, Andrew (1996) The aminolysis and hydrolysis of N-(4,6-diphenoxy-1,3,5-triazin-2-yl) substituted pyridinium salts: Concerted displacement mechanism. Journal of the Chemical Society-Perkin Transactions 2, (8). pp. 1559-1563. ISSN 0300-9580. (doi:10.1039/P29960001559) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:18901)

The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided.
Official URL:
http://dx.doi.org/10.1039/P29960001559

Abstract

Reaction of the title pyridinium salts in aqueous buffers containing amines involves nucleophilic displacement of the pyridine by the amine nitrogen in addition to background hydrolysis. The second-order rate constants for attack of a series of unhindered primary amines on the (4,6-diphenoxy-1,3,5-triazin-2-yl)pyridinium cation obey a Bronsted-like equation with slope beta(nuc) = 0.68. Six-membered-ring cyclic secondary amines have a similar Bronsted selectivity but are approximately 10-fold more reactive than primary amines of similar pK(a). The reactivity of ethanolamine against the title pyridinium salts obeys a Bronsted-like equation with beta(1g) = -0.47. In aminolysis of the triazinyl pyridinium salts the changes in bond fission and bond formation signalled by the polar substituent effects give Leffler alpha(1g) and alpha(nuc) values of 0.38 and 0.54, respectively, which indicate strong coupling between the bonding changes consistent with a concerted process for the displacement reaction. The adduct in the putative stepwise mechanism is considered too reactive to possess a significant barrier for it to exist as a discrete molecule.

Item Type: Article
DOI/Identification number: 10.1039/P29960001559
Subjects: Q Science
Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Physics and Astronomy
Depositing User: M.A. Ziai
Date Deposited: 14 May 2009 19:39 UTC
Last Modified: 16 Nov 2021 09:57 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/18901 (The current URI for this page, for reference purposes)

University of Kent Author Information

Williams, Andrew.

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