Brønsted acid-catalyzed tert-butylation of phenol, o-cresol and catechol: A comparative computational study

Xiaowa Nie, Xin Liu, Chunshan Song, Xinwen Guo

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

SO3H-functionalized ionic liquids (FILs) have been used to catalyze the alkylation of phenol, o-cresol and catechol with tert-butyl alcohol (TBA), and the catalytic performances are promising. During these Brønsted acid-catalyzed tert-butylations, t-butyl phenol ether (TBPE) and t-butyl o-cresol ether (TBOCE) are found, but no t-butyl catechol ether (TBCE) is detected. With the help of density functional theory (DFT) calculations, the reaction mechanisms of Brønsted acid-catalyzed tert-butylation of phenol, o-cresol and catechol were examined. The steric effect of t-butyl group does not have an apparent impact on the regioselectivity to t-butyl ether. The differences in the stability of O-alkylation intermediates, resulted from different ortho-substituents, account for the regioselectivity to t-butyl ether. For catechol tert-butylation, an intramolecular hydrogen bond is formed within the O-alkylation intermediate, which leads to extra stability of this intermediate and obvious increase of the activation barrier for TBCE formation. The intramolecular hydrogen bond formed within the O-alkylation intermediate facilitates its isomerization, inhibits the TBCE formation, thus making the reaction kinetics for catechol tert-butylation unique.

Original languageEnglish (US)
Pages (from-to)145-151
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Volume332
Issue number1-2
DOIs
StatePublished - Nov 1 2010

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

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