Ab initio calculations of the gas-phase elimination kinetics of ethyl oxamate, ethyl oxanilate, and ethyl N,N-dimethyl oxamate

Jose R. Mora, Marcos Antonio Loroño Gonzalez, Tania Cordova, Gabriel Chuchani

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

7 Citas (Scopus)

Resumen

Theoretical studies of the gas-phase elimination kinetics of title compounds were performed by using "ab initio" methods at MP2/6-31G, MP2/6-31G(d,p) and ONIOM [MP2/6-31G (d,p) //MP2/6-31G]. Ethyl Oxamate and ethyl oxanilate undergo a rapid decarbonylation to give the corresponding carbamates. These intermediates proceed to a parallel decomposition to give the corresponding unstable carbamic acid and ethylene through sixmembered cyclic transition state (path 1) and isocyanate and ethanol through a four-membered cyclic transition state (path 2). Ethyl N,N-dimethyloxamate elimination reaction yields in one step, through a six-membered cyclic transition state, dimethyl oxamic acid and ethylene gas. The calculated bond orders, NBO charges and synchronicity indicate that these reactions are concerted and slightly asynchronous. The estimated kinetic and thermodynamic parameters are in good agreement with the reported experimental values.

Idioma originalInglés
Páginas (desde-hasta)503-511
Número de páginas9
PublicaciónJournal of Physical Organic Chemistry
Volumen19
N.º8-9
DOI
EstadoPublicada - ago 2006
Publicado de forma externa

Nota bibliográfica

Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.

Huella

Profundice en los temas de investigación de 'Ab initio calculations of the gas-phase elimination kinetics of ethyl oxamate, ethyl oxanilate, and ethyl N,N-dimethyl oxamate'. En conjunto forman una huella única.

Citar esto