Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis

Lin, Hsi-Hsin; Cheng, Yan; Huo, Jiajie; Shanks, Brent H.

doi:10.1021/acsomega.1c04750

Title: Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis

Journal Article · 27 October 2021 · ACS Omega

DOI: https://doi.org/10.1021/acsomega.1c04750 · OSTI ID:1827751

Lin, Hsi-Hsin ^[1]; Cheng, Yan ^[1]; Huo, Jiajie ^[1];

^[1]

Iowa State Univ., Ames, IA (United States)

Amidation is an important reaction for bioderived platform molecules, which can be upgraded for use in applications such as polymers. However, fundamental understanding of the reaction especially in the presence of multiple groups is still lacking. In this study, the amidation of dimethyl fumarate, maleate, and succinate through ester ammonolysis was examined. The reaction networks and significant side reactions, such as conjugate addition and ring closing, were determined. A preliminary kinetic comparison among additional C₄ and C₆ esters showed a significant correlation between molecular structure and ammonolysis reactivity. Esters with a C=C double bond in the molecule backbone were found to have higher ammonolysis reactivity. To improve the selectivity to unsaturated amides rather than byproducts, the effects of thermal conditions and additives in dimethyl fumarate ammonolysis were examined. Lower temperature and decreasing methoxide ion concentration in the solution relative to the base case conditions increased the fumaramide selectivity from 67.1 to 90.6%.

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Research Organization:: Iowa State Univ., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1827751

Alternate ID(s):: OSTI ID: 1829667

Journal Information:: ACS Omega, Vol. 6, Issue 44; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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