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Title: Catalytic production of methyl acrylates by gold-mediated cross coupling of unsaturated aldehydes with methanol

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:
ORCiD logo [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [4]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Lab.
  3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology, School of Engineering and Applied Sciences
  4. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences
Publication Date:
Report Number(s):
LLNL-JRNL-737636
Journal ID: ISSN 0039-6028
Grant/Contract Number:
AC52-07NA27344; SC0012573
Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 652; Journal Issue: C; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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
OSTI Identifier:
1416497
Alternate Identifier(s):
OSTI ID: 1397443