Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C═C Unsaturation on Reaction Selectivity
| Autor: | Juergen Biener, Branko Zugic, Monika M. Biener, Stavros Karakalos, Kara J. Stowers, Robert J. Madix, Cynthia M. Friend |
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| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Alcohol General Chemistry Reaction intermediate 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound chemistry Organic chemistry Reactivity (chemistry) Methanol Methyl methacrylate Allyl alcohol Methyl acrylate |
| Zdroj: | ACS Catalysis. 6:1833-1839 |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.5b02902 |
| Popis: | Here we demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. Our results clearly show that the C═C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ∼100 and ∼450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than t... |
| Databáze: | OpenAIRE |
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