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A density functional theoretical study of the influence of cavities and water molecules on tautomerism: The case of pyridones and 1,2,4-triazoles linked to crown ethers and esters

✍ Scribed by Ibon Alkorta; José Elguero


Publisher
Journal of Heterocyclic Chemistry
Year
2001
Tongue
English
Weight
82 KB
Volume
38
Category
Article
ISSN
0022-152X

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✦ Synopsis


Abstract

The tautomerism of pyridones and 1,2,4‐triazoles related to two crown ethers and two crown esters derived from these heterocycles was studied theoretically. For the four macrocycles, Bradshaw identified a single tautomer by X‐ray crystallography. To rationalize these findings, a series of calculations from simple models to crown derivatives have been carried out. The most interesting case concerns the observation, for the first time, of a 4H‐1,2,4‐triazole tautomer. To explain this result it was necessary to calculate the whole crown ester plus a caged water molecule was necessary.