Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis
Abstract
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%.
- Authors:
-
[1]
- Department of Chemical and Biological Engineering, Iowa State University, Ames, Iowa 50011, United States, Center for Biorenewable Chemicals (CBiRC), Iowa State University, Ames, Iowa 50011, United States
- Publication Date:
- Research Org.:
- Iowa State Univ., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1827751
- Alternate Identifier(s):
- OSTI ID: 1829667
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- ACS Omega
- Additional Journal Information:
- Journal Name: ACS Omega Journal Volume: 6 Journal Issue: 44; Journal ID: ISSN 2470-1343
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrocarbons; Organic compounds; Selectivity; Molecules; Conjugate acid-base pairs
Citation Formats
Lin, Hsi-Hsin, Cheng, Yan, Huo, Jiajie, and Shanks, Brent H. Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis. United States: N. p., 2021.
Web. doi:10.1021/acsomega.1c04750.
Lin, Hsi-Hsin, Cheng, Yan, Huo, Jiajie, & Shanks, Brent H. Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis. United States. https://doi.org/10.1021/acsomega.1c04750
Lin, Hsi-Hsin, Cheng, Yan, Huo, Jiajie, and Shanks, Brent H. Wed .
"Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis". United States. https://doi.org/10.1021/acsomega.1c04750.
@article{osti_1827751,
title = {Selective Ammonolysis of Bioderived Esters for Biobased Amide Synthesis},
author = {Lin, Hsi-Hsin and Cheng, Yan and Huo, Jiajie and Shanks, Brent H.},
abstractNote = {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%.},
doi = {10.1021/acsomega.1c04750},
journal = {ACS Omega},
number = 44,
volume = 6,
place = {United States},
year = {2021},
month = {10}
}
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