Ab initio and DFT studies on the elimination kinetics 2-substituted ethyl N,N-dimethylcarbamates [(CH3)2NCOOCH2CH2Z, Z=CH2C6H5, C6H5, C(CH3){double bond, short}CH2] in the gas phase

Carlos J. Marcano B, M. Loroño, Tania Córdova, Gabriel Chuchani

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Abstract

The theoretical studies on the elimination kinetics of 2-substituted ethyl N,N-dimethylcarbamates [(CH3)2NCOOCH2CH2Z, Z=CH2C6H5, C6H5, C(CH3){double bond, short}CH2] in the gas phase were carried out using the ab initio MP2/6-31G and DFT RMPWP91/6-31G(d,p) levels of theory. These carbamates produce N,N-dimethylcarbamic acid and the corresponding substituted olefin in a rate determining step. On the basis of these calculations, the mechanism appears to be concerted, asynchronous, through a six-membered cyclic transition state structure. The acidity of the benzylic and allylic β-hydrogen is believed to be responsible for faster elimination rates.

Original languageEnglish
Pages (from-to)201-204
Number of pages4
JournalJournal of Molecular Structure: THEOCHEM
Volume764
Issue number1-3
DOIs
StatePublished - 30 May 2006

Bibliographical note

Copyright:
Copyright 2006 Elsevier B.V., All rights reserved.

Keywords

  • 2-Substituted ethyl N,N-dimethylcarbamates
  • Gas-phase elimination
  • MP2 and DFT RMPWP91 calculations
  • Mechanism
  • Substituent effects

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