Acid catalyzed alkylation of phenols with cyclohexene: Comparison between homogeneous and heterogeneous catalysis, influence of cyclohexyl phenyl ether equilibrium and of the substituent on reaction rate and selectivity
| Autor: | Luigi Toniolo, Lucio Ronchin, Andrea Vavasori |
|---|---|
| Rok vydání: | 2012 |
| Předmět: |
Phenols alkylation
Sulfonated resins Process Chemistry and Technology Aryl Substituent Cyclohexene Ether Alkylation Acid catalysis Alkylation selectivity Heterogeneous catalysis Medicinal chemistry Catalysis chemistry.chemical_compound chemistry Organic chemistry Reactivity (chemistry) Physical and Theoretical Chemistry |
| Zdroj: | Journal of Molecular Catalysis A: Chemical. 355:134-141 |
| ISSN: | 1381-1169 |
| DOI: | 10.1016/j.molcata.2011.12.007 |
| Popis: | a b s t r a c t The reactivity of several phenols toward liquid phase alkylation with cyclohexene in the presence of heterogeneous and homogeneous acid catalyst at 358 K is studied. The comparison between Amberlyst 15 and CH3SO3H, as examples of heterogeneous and homogeneous systems, shows a higher activity of the former with different behavior of selectivity between the two systems, anyway, in both systems O-alkylation and ring alkylations occur. A remarkable difference in the selectivity of the ring alkylation between heterogeneous and homogeneous systems is observed: Amberlyst 15 shows a constant ortho/para ratio close to 2, while in the presence of CH3SO3H ortho/para is variable from 3 to 5, suggesting an involvement of the cyclohexyl phenyl ether rearrangement. This is proved also by a direct relationship between the ortho/para ratio and the concentration of the cyclohexyl phenyl ether when CH3SO3H is used as a catalyst. The formation of cyclohexyl aryl ethers is reversible; on the contrary, ring alkylation appears irreversible. The reactivity of the dimethylphenols shows a strong influence of the steric hindrance of the substituent on the electrophilic attack of the cyclohexyl cation, which is poorly influenced by the inductive effect of the methyl group. © 2011 Published by Elsevier B.V. |
| Databáze: | OpenAIRE |
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