The spontaneous hydrolysis of 2‐pyridyl phosphate is a good model for the special mechanism for the hydrolysis of phosphate monoester monoanions†‡. (2nd August 2013)

• Record Type: Journal Article
• Authors: Medeiros, Michelle; Manfredi, Alex M.; Kirby, Anthony J.; Nome, Faruk; Page, Michael I.
• Is Part Of: Journal of physical organic chemistry. Volume 26:Number 12(2013:Dec.)
• Page Start: 1044
• Page End: 1047
• Publication Date: 2013-08-02
• Subjects: Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3165
• Languages: English
• ISSNs: 0894-3230

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The microscopic p<italic>K</italic>_a of the pyridine N of the phosphate monoester 2‐pyridyl phosphate (MPP) is 2.76, significantly higher than that expected for the leaving group (RO) oxygen of a typical monoester ROPO₃⁼. This favours the prototropic equilibrium considered to be the key step in the rapid <named-content id="d305e517" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">hydrolysis</named-content> of a typical monoester, and the observed rate of <named-content id="d305e520" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">hydrolysis</named-content> of the monoanion MPP⁻ is shown to be close to that expected for the protomer MPP⁺⁼, with neutral 2‐pyridone as the leaving group. Copyright © 2013 John Wiley &amp; Sons, Ltd.</p> </abstract>