کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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56025 | 47069 | 2011 | 9 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Reaction mechanism of tert-butylation of phenol with tert-butyl alcohol over H-β zeolite: An ONIOM study Reaction mechanism of tert-butylation of phenol with tert-butyl alcohol over H-β zeolite: An ONIOM study](/preview/png/56025.png)
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.
Journal: Catalysis Today - Volume 165, Issue 1, 16 May 2011, Pages 120–128