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

Research output: Contribution to journalArticle

7 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)253-262
Number of pages10
JournalApplied Catalysis A: General
Volume240
Issue number1-2
DOIs
Publication statusPublished - 2003 Feb 10

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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

Cite this

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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.

In: Applied Catalysis A: General, Vol. 240, No. 1-2, 10.02.2003, p. 253-262.

Research output: Contribution to journalArticle

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