Reaction mechanism of phenol alkylation with tert-butyl alcohol over Hb zeolite: An ONIOM study

Xiaowa Nie, Xin Liu, Chunshan Song, Min Liu, Xinwen Guo

Research output: Contribution to journalConference article

Abstract

Alkylation of phenol with tert-butyl alcohol (TBA) over Hb zeolite was studied using ONIOM approach with two proposed reaction paths: stepwise and concerted mechanisms. The computational results obtained by the ONIOM (B3LYP/6-31G(d,p):UFF) method revealed that the reaction preferentially occurs through a concerted mechanism rather than via the stepwise mechanism. The reactivity difference between the 2- and 4-tert-butylation became more apparent in the concerted mechanism where the 2-tert-butylation proceeded faster. The reaction activation energies of the 2- and 4-tert-butylation were predicted to be 110.7 and 121.9kJ/mol, respectively. In the stepwise mechanism, the formation of the tert-butyl carbenium species was the rate-limiting step. In the subsequent tert-butylation process, phenol tert-butylation was faster than the tert-butyl carbenium formation, with the activation energies of 94.3 and 99.3 kJ/mol for the 2- and 4-tert-butylation, respectively. It was found that 2-tert-butyl phenol was a kinetically favored product, whereas 4-tert-butyl phenol was the thermodynamically most preferred product.

Original languageEnglish (US)
JournalACS National Meeting Book of Abstracts
StatePublished - Dec 1 2010
Event239th ACS National Meeting and Exposition - San Francisco, CA, United States
Duration: Mar 21 2010Mar 25 2010

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tert-Butyl Alcohol
Zeolites
Alkylation
Phenol
Phenols
Alcohols
Activation energy

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

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title = "Reaction mechanism of phenol alkylation with tert-butyl alcohol over Hb zeolite: An ONIOM study",
abstract = "Alkylation of phenol with tert-butyl alcohol (TBA) over Hb zeolite was studied using ONIOM approach with two proposed reaction paths: stepwise and concerted mechanisms. The computational results obtained by the ONIOM (B3LYP/6-31G(d,p):UFF) method revealed that the reaction preferentially occurs through a concerted mechanism rather than via the stepwise mechanism. The reactivity difference between the 2- and 4-tert-butylation became more apparent in the concerted mechanism where the 2-tert-butylation proceeded faster. The reaction activation energies of the 2- and 4-tert-butylation were predicted to be 110.7 and 121.9kJ/mol, respectively. In the stepwise mechanism, the formation of the tert-butyl carbenium species was the rate-limiting step. In the subsequent tert-butylation process, phenol tert-butylation was faster than the tert-butyl carbenium formation, with the activation energies of 94.3 and 99.3 kJ/mol for the 2- and 4-tert-butylation, respectively. It was found that 2-tert-butyl phenol was a kinetically favored product, whereas 4-tert-butyl phenol was the thermodynamically most preferred product.",
author = "Xiaowa Nie and Xin Liu and Chunshan Song and Min Liu and Xinwen Guo",
year = "2010",
month = "12",
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language = "English (US)",
journal = "ACS National Meeting Book of Abstracts",
issn = "0065-7727",
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Reaction mechanism of phenol alkylation with tert-butyl alcohol over Hb zeolite : An ONIOM study. / Nie, Xiaowa; Liu, Xin; Song, Chunshan; Liu, Min; Guo, Xinwen.

In: ACS National Meeting Book of Abstracts, 01.12.2010.

Research output: Contribution to journalConference article

TY - JOUR

T1 - Reaction mechanism of phenol alkylation with tert-butyl alcohol over Hb zeolite

T2 - An ONIOM study

AU - Nie, Xiaowa

AU - Liu, Xin

AU - Song, Chunshan

AU - Liu, Min

AU - Guo, Xinwen

PY - 2010/12/1

Y1 - 2010/12/1

N2 - Alkylation of phenol with tert-butyl alcohol (TBA) over Hb zeolite was studied using ONIOM approach with two proposed reaction paths: stepwise and concerted mechanisms. The computational results obtained by the ONIOM (B3LYP/6-31G(d,p):UFF) method revealed that the reaction preferentially occurs through a concerted mechanism rather than via the stepwise mechanism. The reactivity difference between the 2- and 4-tert-butylation became more apparent in the concerted mechanism where the 2-tert-butylation proceeded faster. The reaction activation energies of the 2- and 4-tert-butylation were predicted to be 110.7 and 121.9kJ/mol, respectively. In the stepwise mechanism, the formation of the tert-butyl carbenium species was the rate-limiting step. In the subsequent tert-butylation process, phenol tert-butylation was faster than the tert-butyl carbenium formation, with the activation energies of 94.3 and 99.3 kJ/mol for the 2- and 4-tert-butylation, respectively. It was found that 2-tert-butyl phenol was a kinetically favored product, whereas 4-tert-butyl phenol was the thermodynamically most preferred product.

AB - Alkylation of phenol with tert-butyl alcohol (TBA) over Hb zeolite was studied using ONIOM approach with two proposed reaction paths: stepwise and concerted mechanisms. The computational results obtained by the ONIOM (B3LYP/6-31G(d,p):UFF) method revealed that the reaction preferentially occurs through a concerted mechanism rather than via the stepwise mechanism. The reactivity difference between the 2- and 4-tert-butylation became more apparent in the concerted mechanism where the 2-tert-butylation proceeded faster. The reaction activation energies of the 2- and 4-tert-butylation were predicted to be 110.7 and 121.9kJ/mol, respectively. In the stepwise mechanism, the formation of the tert-butyl carbenium species was the rate-limiting step. In the subsequent tert-butylation process, phenol tert-butylation was faster than the tert-butyl carbenium formation, with the activation energies of 94.3 and 99.3 kJ/mol for the 2- and 4-tert-butylation, respectively. It was found that 2-tert-butyl phenol was a kinetically favored product, whereas 4-tert-butyl phenol was the thermodynamically most preferred product.

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