Bronsted acid-catalyzed tert-butylation of phenol, o-cresol and catechol: A comparative computational study
发布时间：2019-03-09
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- 论文类型：
- 期刊论文
- 发表时间：
- 2010-11-01
- 发表刊物：
- JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
- 收录刊物：
- Scopus、EI、SCIE
- 文献类型：
- J
- 卷号：
- 332
- 期号：
- 1-2
- 页面范围：
- 145-151
- ISSN号：
- 1381-1169
- 关键字：
- Phenol; o-Cresol; Catechol; Bronsted acid-catalyzed tert-butylation; Density functional theory
- 摘要：
- SO(3)H-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 Bronsted 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 Bronsted 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. (C) 2010 Elsevier B.V. All rights reserved.
- 第一作者
- Nie, Xiaowa
- 合写作者
- Song, Chunshan,Guo, Xinwen,Liu, Xin
- 通讯作者
- Song, CS (reprint author), Dalian Univ Technol, Sch Chem Engn, Dept Catalysis Chem & Engn, State Key Lab Fine Chem, POB 39,158 Zhongshan Rd, Dalian 116012, Peoples R China.