Reaction mechanism of tert-butylation of phenol with tert-butyl alcohol over H-β zeolite: An ONIOM study

Xiaowa Nie, Michael J. Janik, Xinwen Guo, Xin Liu, Chunshan Song

Research output: Contribution to journalArticle

15 Scopus citations

Abstract

Tert-butylation of phenol with tert-butyl alcohol (TBA) over H-β zeolite was studied using the ONIOM approach with two proposed reaction paths: stepwise and concerted mechanisms. The results obtained by the ONIOM2 (B3LYP/6-31G(d,p):UFF) method reveals that the tert-butylation of phenol preferentially occurs through a co-adsorbed, concerted mechanism without prior dehydration of tert-butyl alcohol, rather than via a stepwise mechanism through dehydration to form tert-butyl carbenium ion as the first step followed by tert-butyl cation attack on the 2- or 4-position on phenol. The kinetic difference between 2- and 4-tert-butylation is more apparent in the concerted path, where 4-tert-butylation proceeds over a lower activation barrier. Decreasing the acid site strength, via substitution of Ga for Al, reduces the H-bonding interaction between the zeolitic proton and tert-butyl alcohol and increases the apparent activation barriers, which slows the overall reaction, and also lowers the selectivity to 4-tert-butyl phenol.

Original languageEnglish (US)
Pages (from-to)120-128
Number of pages9
JournalCatalysis Today
Volume165
Issue number1
DOIs
StatePublished - May 16 2011

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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