The influence of steric and electronic effects on the preparation of cyclic acetals catalyzed by sulfated metal oxides

Chiu-Hsun Lin, Shawn D. Lin, Tsung Po Lin, Ya Jean Huang

研究成果: Article

7 引文 (Scopus)

摘要

Sulfated metal oxides (SMO) were able to catalyze the reaction of carbonyl compounds with ethylene glycol (EG), producing cyclic acetals at near ambient temperature. Sulfated hafnium oxide containing only Lewis acid sites (indicated by IR/pyridine adsorption experiments) was found active for the reaction. However, these Lewis acid sites might not be the active sites for the reaction, because they were most likely transformed into Bronsted acid sites by water produced in the reaction. Both electronic and steric effects played important roles in this reaction. The sulfate group coordinating to the active acid site had exerted a steric influence on the reaction. Therefore, the less bulky cyclic acetals were more readily formed. The carbonyl group conjugated with a double bond delocalized the positive charge on the carbocation reaction intermediate, resulting in lower cyclic acetal yields.

原文English
頁(從 - 到)253-262
頁數10
期刊Applied Catalysis A: General
240
發行號1-2
DOIs
出版狀態Published - 2003 二月 10

指紋

Acetals
Oxides
Lewis Acids
Metals
Acids
Carbonyl compounds
Reaction intermediates
Ethylene Glycol
Hafnium oxides
Sulfates
Ethylene glycol
Pyridine
Adsorption
Water
Experiments
Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology

引用此文

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abstract = "Sulfated metal oxides (SMO) were able to catalyze the reaction of carbonyl compounds with ethylene glycol (EG), producing cyclic acetals at near ambient temperature. Sulfated hafnium oxide containing only Lewis acid sites (indicated by IR/pyridine adsorption experiments) was found active for the reaction. However, these Lewis acid sites might not be the active sites for the reaction, because they were most likely transformed into Bronsted acid sites by water produced in the reaction. Both electronic and steric effects played important roles in this reaction. The sulfate group coordinating to the active acid site had exerted a steric influence on the reaction. Therefore, the less bulky cyclic acetals were more readily formed. The carbonyl group conjugated with a double bond delocalized the positive charge on the carbocation reaction intermediate, resulting in lower cyclic acetal yields.",
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The influence of steric and electronic effects on the preparation of cyclic acetals catalyzed by sulfated metal oxides. / Lin, Chiu-Hsun; Lin, Shawn D.; Lin, Tsung Po; Huang, Ya Jean.

於: Applied Catalysis A: General, 卷 240, 編號 1-2, 10.02.2003, p. 253-262.

研究成果: Article

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AB - Sulfated metal oxides (SMO) were able to catalyze the reaction of carbonyl compounds with ethylene glycol (EG), producing cyclic acetals at near ambient temperature. Sulfated hafnium oxide containing only Lewis acid sites (indicated by IR/pyridine adsorption experiments) was found active for the reaction. However, these Lewis acid sites might not be the active sites for the reaction, because they were most likely transformed into Bronsted acid sites by water produced in the reaction. Both electronic and steric effects played important roles in this reaction. The sulfate group coordinating to the active acid site had exerted a steric influence on the reaction. Therefore, the less bulky cyclic acetals were more readily formed. The carbonyl group conjugated with a double bond delocalized the positive charge on the carbocation reaction intermediate, resulting in lower cyclic acetal yields.

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