From 2-Hydroxypyridine to 4(3H)-Pyrimidinone: Computational Study on the Control of the Tautomeric Equilibrium

• Type: Article in International Scientific Journal
• Date: 2013

Authors

Tiago L P Galvao (Author) Other; Ines M Rocha (Author) Other; Maria D M C R Ribeiro da Silva (Author) FCUP; Manuel A V R Ribeiro da Silva (Author) Other

Journal

Title: Journal of Physical Chemistry A

Vol. 117

Pages: 12668-12674

ISSN: 1089-5639

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 28 Citations

Scopus - 31 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-006-JH3

DOI: 10.1021/jp410004x

Abstract (EN): In this work is investigated why the entrance of a nitrogen atom in the ring of cis-2-hydroxypyridine and 2-pyridinone, resulting in cis-4-hydroxypyrimidine and 4(3H)-pyrimidinone, respectively, shifts the tautomeric equilibrium from the hydroxyl form, in the pyridine derivative, to the ketonic form, in the pyrimidine derivative. The conclusions obtained for these model systems allow us to understand how to control the gaseous-phase keto enol tautomeric equilibrium in nitrogen heterocyclic rings and justify the tautomeric preference in pyrimidine nucleobases. The experimental and computational energetics of tautomeric equilibrium were interpreted in terms of the aromaticity, intramolecular hydrogen bonds, and electronic delocalization, evaluated using nucleus independent chemical shifts, quantum theory of atoms in molecules, natural bond orbital analysis, and the thermodynamic changes of appropriate reactions.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 7