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

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7 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)503-511
Number of pages9
JournalJournal of Physical Organic Chemistry
Volume19
Issue number8-9
DOIs
StatePublished - Aug 2006
Externally publishedYes

Bibliographical note

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

Keywords

  • "ab initio" calculations
  • Ethyl N,N-dimethyl oxamate
  • Ethyl oxamate
  • Ethyl oxanilate
  • Kinetics
  • Pyrolysis
  • Reaction mechanism
  • Transition-state structure
  • Unimolecular elimination

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