Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol
Abstract
Modern methods of esterification, one of the most important reactions in organic synthesis, are reaching their limits, as far as waste and expense are concerned. Novel chemical approaches to ester formation are therefore of importance. We report a simple procedure free of caustic reagents or byproducts for the facile direct oxidative methyl esterification of aldehydes over nanoporous Au catalysts. Complementary model studies on single crystal gold surfaces establish the fundamental reactions involved. We also find that methanol more readily reacts with adsorbed active oxygen than do the aldehydes, but that once the aldehydes do react, they form strongly-bound acrylates that block reactive sites and decrease the yields of acrylic esters under steady flow conditions at 420 K. We can achieve significant improvements in yield by operating at higher temperatures, which render the site-blocking acrylates unstable.
- Authors:
-
[1];
- Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
- Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, School of Engineering and Applied Sciences
- Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1416497
- Alternate Identifier(s):
- OSTI ID: 1397443
- Report Number(s):
- LLNL-JRNL-737636
Journal ID: ISSN 0039-6028
- Grant/Contract Number:
- AC52-07NA27344; SC0012573
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 652; Journal Issue: C; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; aldehyde esterification; oxidative cross-coupling; methyl acrylate production; nanoporous gold; gold; Au(110); selective oxidation
Citation Formats
Karakalos, Stavros, Zugic, Branko, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Madix, Robert J. Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol. United States: N. p., 2016.
Web. doi:10.1016/j.susc.2016.03.017.
Karakalos, Stavros, Zugic, Branko, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Friend, Cynthia M., & Madix, Robert J. Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol. United States. https://doi.org/10.1016/j.susc.2016.03.017
Karakalos, Stavros, Zugic, Branko, Stowers, Kara J., Biener, Monika M., Biener, Juergen, Friend, Cynthia M., and Madix, Robert J. Fri .
"Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol". United States. https://doi.org/10.1016/j.susc.2016.03.017. https://www.osti.gov/servlets/purl/1416497.
@article{osti_1416497,
title = {Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol},
author = {Karakalos, Stavros and Zugic, Branko and Stowers, Kara J. and Biener, Monika M. and Biener, Juergen and Friend, Cynthia M. and Madix, Robert J.},
abstractNote = {Modern methods of esterification, one of the most important reactions in organic synthesis, are reaching their limits, as far as waste and expense are concerned. Novel chemical approaches to ester formation are therefore of importance. We report a simple procedure free of caustic reagents or byproducts for the facile direct oxidative methyl esterification of aldehydes over nanoporous Au catalysts. Complementary model studies on single crystal gold surfaces establish the fundamental reactions involved. We also find that methanol more readily reacts with adsorbed active oxygen than do the aldehydes, but that once the aldehydes do react, they form strongly-bound acrylates that block reactive sites and decrease the yields of acrylic esters under steady flow conditions at 420 K. We can achieve significant improvements in yield by operating at higher temperatures, which render the site-blocking acrylates unstable.},
doi = {10.1016/j.susc.2016.03.017},
journal = {Surface Science},
number = C,
volume = 652,
place = {United States},
year = {Fri Mar 18 00:00:00 EDT 2016},
month = {Fri Mar 18 00:00:00 EDT 2016}
}
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Works referencing / citing this record:
Bio‐Acrylates Production: Recent Catalytic Advances and Perspectives of the Use of Lactic Acid and Their Derivates
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