Theoretical calculations for neighboring group participation in gas-phase elimination kinetics of 2-hydroxyphenethyl chloride and 2-methoxyphenethyl chloride

Yannely Brusco, Neydher Berroteran, Marcos Antonio Loroño Gonzalez, Tania Córdova, Gabriel Chuchani

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9 Scopus citations

Abstract

Theoretical calculation of the kinetics and mechanisms of gas-phase elimination of 2-hydroxyphenethyl chloride and 2-methoxyphenethyl chloride has been carried out at the MP2/6-31G(d,p), B3LYP/6-31G(d,p), B3LYP/6-31 +G(d,p), B3PW91/6-31G(d,p) and CCSD(T) levels of the theory. The two substrates undergo parallel elimination reactions. The first process of elimination appears to proceed through a three-membered cyclic transition state by the anchimeric assistance of the aromatic ring to produce the corresponding styrene product and HCl. The second process of elimination occurs through a five-membered cyclic transition state by participation of the oxygen of o-OH or the o-OCH3 to yield in both cases benzohydrofuran. The B3PW91/6-31G(d,p) method was found to be in good agreement with the experimental kinetic and thermodynamic parameters for both substrates in the two reaction channels. However, some differences in the performance of the different methods are observed. NBO analysis of the pyrolysis of both phenethyl chlorides implies a C-Cl bond polarization, in the sense of Cδ + Clδ -, which is a rate-determining step for both parallel reactions. Synchronicity parameters imply polar transition states of these elimination reactions.

Original languageEnglish
Pages (from-to)1022-1029
Number of pages8
JournalJournal of Physical Organic Chemistry
Volume22
Issue number11
DOIs
StatePublished - Nov 2009
Externally publishedYes

Bibliographical note

Copyright:
Copyright 2009 Elsevier B.V., All rights reserved.

Keywords

  • 2-hydroxyphenethyl chloride
  • 2-methoxyphenethyl chloride
  • Ab initio
  • DFT calculations
  • Gas-phase elimination
  • Kinetic
  • Mechanism

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