Theoretical study of methoxy group influence in the gas-phase elimination kinetics of methoxyalkyl chlorides

Oriana Brea, Marcos Antonio Loroño Gonzalez, Edgar Marquez, Jose R. Mora, Tania Cordova, Gabriel Chuchani

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

The unimolecular gas-phase elimination kinetics of 2-methoxy-1- chloroethane, 3-methoxy-1-chloropropane, and 4-methoxyl-1-chloroburane has been studied by using density functional theory (DFT) methods to propose the most reasonable mechanisms of decomposition of the aforementioned compounds. Calculation results of 2-methoxy-1-chloroethane and 3-methoxy-1-chloropropane suggest dehydrochlorination through a concerted nonsynchronous four-centered cyclic transition state (TS) to give the corresponding olefin. In the case of 4-methoxyl-1-chloroburane, in addition to the 1,2-elimination mechanism, the anchimeric assistance by the methoxy group, through a polar five-centered cyclic TS, provides additional pathways to give 4-methoxy-butene, tetrahydrofuran and chloromethane. The bond polarization of the C-Cl, in the direction of C δ+···Cl δ -, is the limiting step of these elimination reactions. The significant increase in rate together with the formation of a cyclic product tetrahydrofuran in the gas-phase elimination of 4-methoxyl-1-chloroburane is attributed to neighboring group participation of the oxygen of the methoxy group in the TS. The theoretical calculations show a good agreement with the reported experimental results.

Original languageEnglish
Pages (from-to)2504-2514
Number of pages11
JournalInternational Journal of Quantum Chemistry
Volume112
Issue number12
DOIs
StatePublished - 15 Jun 2012
Externally publishedYes

Bibliographical note

Copyright:
Copyright 2012 Elsevier B.V., All rights reserved.

Keywords

  • 2-methoxy-1-chloroethane 3-methoxy-1-chloropropane
  • 4-methoxyl-1- chloroburane
  • DFT calculations
  • gas-phase elimination
  • kinetics

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