DFT study of the gas‐phase thermal decomposition kinetics of 2‐ethoxypyridine into 2‐pyridone |
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| Authors: | Edgar Marquez Tania Cordova Gabriel Chuchani |
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| Affiliation: | 1. Departamento de Química, Escuela de Ciencias, Universidad de Oriente Núcleo Sucre, Cumana, Venezuela;2. Department of Medicinal Chemistry, College of Pharmacy, University of Florida, P.O Box. 100485, Gainesville, FL 32610;3. Centro de Química, Instituto Venezolano de Investigaciones Científicas (I.V.I.C.), Apartado 21827, Caracas 1020.A, Venezuela |
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| Abstract: | The mechanism of the gas‐phase elimination kinetics of 2‐ethoxypyridine has been studied through the electronic structure calculations using density functional methods: B3LYP/6‐31G(d,p), B3LYP/6‐31++G(d,p), B3PW91/6‐31G(d,p), B3PW91/6‐31++G(d,p), MPW1PW91/6‐31G(d,p), MPW1PW91/6‐31++G(d,p), PBEPBE/6‐31G(d,p), PBEPBE/6‐31++G(d,p), PBE1PBE1/6‐31G(d,p), and PBE1PBE1/6‐31++G(d,p). The elimination reaction of 2‐ethoxypyridine occurs through a six‐centered transition state geometry involving the pyridine nitrogen, the substituted carbon of the aromatic ring, the ethoxy oxygen, two carbons of the ethoxy group, and a hydrogen atom, which migrates from the ethoxy group to the nitrogen to give 2‐pyridone and ethylene. The reaction mechanism appears to occur with the participation of π‐electrons, similar to alkyl vinyl ether elimination reaction, with simultaneous ethylene formation and hydrogen migration to the pyridine nitrogen producing 2‐pyridone. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 |
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| Keywords: | 2‐ethoxypyridine mechanism gas‐phase elimination DFT calculations |
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