Iodine-Catalyzed Isomerization of Dimethyl Muconate
Abstract
Abstract cis,cis ‐Muconic acid is a platform bio‐based chemical that can be upgraded to drop‐in commodity and novel monomers. Among the possible drop‐in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels–Alder cycloaddition, and dehydrogenation. The isomerization of cis , cis ‐dimethyl muconate ( cc DMM) to the trans , trans ‐form ( tt DMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high‐purity tt DMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine‐catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations owing to the large number of halogen‐diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely because of solvent complexation with iodine. Under select conditions, tt DMM yields of 95 % were achieved in <1 h with methanol, followed by high purity recovery (>98 %) with crystallization. Lastly, post‐reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary formore »
- Authors:
-
[1];
[2];
[1];
[2];
[2];
[1]
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1436570
- Alternate Identifier(s):
- OSTI ID: 1436543
- Report Number(s):
- NREL/JA-5100-71487
Journal ID: ISSN 1864-5631
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Volume: 11; Journal ID: ISSN 1864-5631
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; platform chemicals; reaction mechanism; green chemistry; biomass conversion
Citation Formats
Settle, Amy E., Berstis, Laura, Zhang, Shuting, Rorrer, Nicholas A., Hu, Haiming, Richards, Ryan M., Beckham, Gregg T., Crowley, Michael F., and Vardon, Derek R. Iodine-Catalyzed Isomerization of Dimethyl Muconate. United States: N. p., 2018.
Web. doi:10.1002/cssc.201800606.
Settle, Amy E., Berstis, Laura, Zhang, Shuting, Rorrer, Nicholas A., Hu, Haiming, Richards, Ryan M., Beckham, Gregg T., Crowley, Michael F., & Vardon, Derek R. Iodine-Catalyzed Isomerization of Dimethyl Muconate. United States. https://doi.org/10.1002/cssc.201800606
Settle, Amy E., Berstis, Laura, Zhang, Shuting, Rorrer, Nicholas A., Hu, Haiming, Richards, Ryan M., Beckham, Gregg T., Crowley, Michael F., and Vardon, Derek R. Mon .
"Iodine-Catalyzed Isomerization of Dimethyl Muconate". United States. https://doi.org/10.1002/cssc.201800606. https://www.osti.gov/servlets/purl/1436570.
@article{osti_1436570,
title = {Iodine-Catalyzed Isomerization of Dimethyl Muconate},
author = {Settle, Amy E. and Berstis, Laura and Zhang, Shuting and Rorrer, Nicholas A. and Hu, Haiming and Richards, Ryan M. and Beckham, Gregg T. and Crowley, Michael F. and Vardon, Derek R.},
abstractNote = {Abstract cis,cis ‐Muconic acid is a platform bio‐based chemical that can be upgraded to drop‐in commodity and novel monomers. Among the possible drop‐in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels–Alder cycloaddition, and dehydrogenation. The isomerization of cis , cis ‐dimethyl muconate ( cc DMM) to the trans , trans ‐form ( tt DMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high‐purity tt DMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine‐catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations owing to the large number of halogen‐diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely because of solvent complexation with iodine. Under select conditions, tt DMM yields of 95 % were achieved in <1 h with methanol, followed by high purity recovery (>98 %) with crystallization. Lastly, post‐reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state‐of‐the‐art for bio‐based chemicals.},
doi = {10.1002/cssc.201800606},
journal = {ChemSusChem},
number = ,
volume = 11,
place = {United States},
year = {Mon Apr 16 00:00:00 EDT 2018},
month = {Mon Apr 16 00:00:00 EDT 2018}
}
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Works referencing / citing this record:
Across the Board: Mark Mascal on the Challenges of Lignin Biorefining
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