Iodine-Catalyzed Isomerization of Dimethyl Muconate
Abstract
cis,cis-Muconic acid is a platform biobased 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 (ccDMM) to the trans,trans-form (ttDMM) 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 ttDMM. 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 due 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 due to solvent complexation with iodine. Under select conditions, ttDMM 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. Altogether, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.
- 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 Lab. (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 = {cis,cis-Muconic acid is a platform biobased 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 (ccDMM) to the trans,trans-form (ttDMM) 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 ttDMM. 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 due 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 due to solvent complexation with iodine. Under select conditions, ttDMM 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. Altogether, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.},
doi = {10.1002/cssc.201800606},
journal = {ChemSusChem},
number = ,
volume = 11,
place = {United States},
year = {2018},
month = {4}
}
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Works referenced in this record:
Kinetics and mechanism of the reaction of iodine with tetrahydrofuran. Carbon-hydrogen bond dissociation energy in tetrahydrofuran
journal, March 1969
- Cruickshank, Frank R.; Benson, Sidney W.
- Journal of the American Chemical Society, Vol. 91, Issue 6
Solvent Effects in the Iodide-Iodine-Triiodide Complex Equilibrium 1
journal, April 1954
- Katzin, Leonard I.; Gebert, Elizabeth
- Journal of the American Chemical Society, Vol. 76, Issue 8
Use of a free radical method to evaluate antioxidant activity
journal, January 1995
- Brand-Williams, W.; Cuvelier, M. E.; Berset, C.
- LWT - Food Science and Technology, Vol. 28, Issue 1
Iodine-photocatalyzed cis-trans Isomerization of Stilbene
journal, July 1961
- Yamashita, Shigeru
- Bulletin of the Chemical Society of Japan, Vol. 34, Issue 7
Glucose-Free cis , cis -Muconic Acid Production via New Metabolic Designs Corresponding to the Heterogeneity of Lignin
journal, November 2017
- Sonoki, Tomonori; Takahashi, Kenji; Sugita, Haruka
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 1
Iodine-Catalyzed R / S Isomerization of Allenic Carotenoids
journal, March 2002
- He, Zhangfei; Gao, Guoqiang; Hand, Elli S.
- The Journal of Physical Chemistry A, Vol. 106, Issue 11
LED based NMR illumination device for mechanistic studies on photochemical reactions – Versatile and simple, yet surprisingly powerful
journal, July 2013
- Feldmeier, C.; Bartling, H.; Riedle, E.
- Journal of Magnetic Resonance, Vol. 232
Photodissociation and recombination dynamics of iodine molecule(1-) in solution
journal, October 1992
- Johnson, Alan E.; Levinger, Nancy E.; Barbara, Paul F.
- The Journal of Physical Chemistry, Vol. 96, Issue 20
Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar
journal, January 2016
- Suastegui, Miguel; Matthiesen, John E.; Carraher, Jack M.
- Angewandte Chemie International Edition, Vol. 55, Issue 7
cis,cis-Muconic acid isomerization and catalytic conversion to biobased cyclic-C 6 -1,4-diacid monomers
journal, January 2017
- Carraher, Jack M.; Pfennig, Toni; Rao, Radhika G.
- Green Chemistry, Vol. 19, Issue 13
Iodine-Catalyzed Isomerization of Olefins. I. Thermodynamic Data from Equilibrium Studies of Positional and Geometrical Isomerization of 1-Butene and 2-Butene
journal, December 1964
- Golden, David M.; Egger, Kurt W.; Benson, Sidney W.
- Journal of the American Chemical Society, Vol. 86, Issue 24
Iodine-Catalyzed Isomerization of Olefins. II. The Resonance Energy of the Allyl Radical and the Kinetics of the Positional Isomerization of 1-Butene
journal, December 1964
- Egger, Kurt W.; Golden, David M.; Benson, Sidney W.
- Journal of the American Chemical Society, Vol. 86, Issue 24
Analysis of iodine species in aqueous solutions
journal, March 2003
- Bruchertseifer, H.; Cripps, R.; Guentay, S.
- Analytical and Bioanalytical Chemistry, Vol. 375, Issue 8
Iodine catalysis: A green alternative to transition metals in organic chemistry and technology
journal, July 2015
- Yusubov, Mekhman S.; Zhdankin, Viktor V.
- Resource-Efficient Technologies, Vol. 1, Issue 1
Molecular Complexes and their Spectra. XV. Iodine Complexes with Thiophene, 2-Methylfuran and N-Methylpyrrole
journal, December 1962
- Lang, Robert P.
- Journal of the American Chemical Society, Vol. 84, Issue 23
Photocatalysis with solar energy at a pilot-plant scale: an overview
journal, April 2002
- Malato, Sixto; Blanco, Julián; Vidal, Alfonso
- Applied Catalysis B: Environmental, Vol. 37, Issue 1
Exploring the unexpected pyridine- and 4,4′-bipyridine-catalyzed isomerization of maleic acid: A DFT approach
journal, May 2012
- Karaman, Rafik
- Computational and Theoretical Chemistry, Vol. 988
Corrosion of Steel by Iodine
journal, November 1968
- Ochar, D. R.; Vermilyea, D. A.
- CORROSION, Vol. 24, Issue 11
The Absorption Spectrum of the Iodine Atom
journal, June 1934
- McLeod, J. H.
- Physical Review, Vol. 45, Issue 11
XSEDE: Accelerating Scientific Discovery
journal, September 2014
- Towns, John; Cockerill, Timothy; Dahan, Maytal
- Computing in Science & Engineering, Vol. 16, Issue 5
cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization
journal, January 2016
- Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia
- Green Chemistry, Vol. 18, Issue 11
Gas-phase molecular complexes. The furan-iodine charge-transfer complex
journal, August 1967
- Ginns, Edward I.; Strong, Robert L.
- The Journal of Physical Chemistry, Vol. 71, Issue 9
Iodine-Catalyzed Isomerization of Olefins. III. Kinetics of the Geometrical Isomerization of Butene-2 and the Rate of Rotation About a Single Bond
journal, February 1965
- Benson, Sidney W.; Egger, Kurt W.; Golden, David M.
- Journal of the American Chemical Society, Vol. 87, Issue 3
The Equilibrium and Kinetics of the Thermal Isomerization of Dichloroethylene Catalyzed by Iodine
journal, December 1939
- Wood, Reuben E.; Dickinson, Roscoe G.
- Journal of the American Chemical Society, Vol. 61, Issue 12
Mechanism of Cis/Trans Equilibration of Alkenes via Iodine Catalysis
journal, December 2005
- Hepperle, Steven S.; Li, Qingbin; East, Allan L. L.
- The Journal of Physical Chemistry A, Vol. 109, Issue 48
Industrial exploitation of photocatalysis: progress, perspectives and prospects
journal, December 2004
- Adesina, A. A.
- Catalysis Surveys from Asia, Vol. 8, Issue 4
Synthesis of ethylene glycol and terephthalic acid from biomass for producing PET
journal, January 2016
- Pang, Jifeng; Zheng, Mingyuan; Sun, Ruiyan
- Green Chemistry, Vol. 18, Issue 2
Donor–acceptor interaction between non-aqueous solvents and I2 to generate I−3, and its implication in dye sensitized solar cells
journal, March 1999
- Kebede, Zerihun; Lindquist, Sten-Eric
- Solar Energy Materials and Solar Cells, Vol. 57, Issue 3
A review on UV/TiO2 photocatalytic oxidation process (Journal Review)
journal, January 2008
- Thiruvenkatachari, Ramesh; Vigneswaran, Saravanamuthu; Moon, Il Shik
- Korean Journal of Chemical Engineering, Vol. 25, Issue 1
The thermodynamic equilibrium between cis- and trans-isomers in stilbene and some derivatives
journal, January 1968
- Fischer, Gabriella; Muszkat, K. A.; Fischer, Ernst
- Journal of the Chemical Society B: Physical Organic
Chemistry of halogens and a polyhalides. XXX. Influence of solvent properties on the formation of pyridine-iodine charge-transfer complexes
journal, September 1969
- McKinney, William J.; Popov, Alexander I.
- Journal of the American Chemical Society, Vol. 91, Issue 19
What is a green solvent? A comprehensive framework for the environmental assessment of solvents
journal, January 2007
- Capello, Christian; Fischer, Ulrich; Hungerbühler, Konrad
- Green Chemistry, Vol. 9, Issue 9
Production of Diethyl Terephthalate from Biomass-Derived Muconic Acid
journal, November 2015
- Lu, Rui; Lu, Fang; Chen, Jiazhi
- Angewandte Chemie International Edition, Vol. 55, Issue 1
Review of Major Design and Scale-up Considerations for Solar Photocatalytic Reactors
journal, October 2009
- Braham, Rowan J.; Harris, Andrew T.
- Industrial & Engineering Chemistry Research, Vol. 48, Issue 19
Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014
- Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
- Science, Vol. 344, Issue 6185, p. 1246843-1246843
Thermal cis-trans isomerization of butadiene
journal, November 1972
- Stephenson, L. M.; Gemmer, R. V.; Brauman, John I.
- Journal of the American Chemical Society, Vol. 94, Issue 24
Performance of the major semiempirical, ab initio, and DFT methods for isomerization enthalpies of linear to branched heptanes
journal, March 2016
- Rayne, Sierra; Forest, Kaya
- Journal of Environmental Science and Health, Part A, Vol. 51, Issue 7
Computational study of the ground state properties of iodine and polyiodide ions
journal, November 2008
- Md Asaduzzaman, Abu; Schreckenbach, Georg
- Theoretical Chemistry Accounts, Vol. 122, Issue 3-4
Molecular iodine-catalyzed efficient and highly rapid synthesis of bis(indolyl)methanes under mild conditions
journal, February 2003
- Bandgar, B. P.; Shaikh, K. A.
- Tetrahedron Letters, Vol. 44, Issue 9
Across the Board: Pieter Bruijnincx
journal, May 2016
- Bruijnincx, Pieter C. A.
- ChemSusChem, Vol. 9, Issue 10
A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons
journal, August 1949
- Benesi, H. A.; Hildebrand, J. H.
- Journal of the American Chemical Society, Vol. 71, Issue 8
Comparative study of kinetics isomerization of substituted polyacetylene (Cl, F and I): Ab initio and DFT calculations
journal, October 2012
- Djebaili, Abdelbaki; Labidi, Nouar Sofiane
- Journal of Saudi Chemical Society, Vol. 16, Issue 4
Bioderived Muconates by Cross-Metathesis and Their Conversion into Terephthalates
journal, January 2018
- Saraçi, Erisa; Wang, Lan; Theopold, Klaus H.
- ChemSusChem, Vol. 11, Issue 4
Iodine-Catalyzed Regioselective Sulfenylation of Indoles with Sulfonyl Hydrazides
journal, March 2013
- Yang, Fu-Lai; Tian, Shi-Kai
- Angewandte Chemie, Vol. 125, Issue 18
Some aspects of cis – trans -isomerization mechanisms
journal, March 1968
- Lin, M. C.; Laidler, K. J.
- Canadian Journal of Chemistry, Vol. 46, Issue 6
Iodine/Visible Light Photocatalysis for Activation of Alkynes for Electrophilic Cyclization Reactions
journal, May 2017
- Liu, Yuliang; Wang, Bin; Qiao, Xiaofeng
- ACS Catalysis, Vol. 7, Issue 6
Renewable Unsaturated Polyesters from Muconic Acid
journal, October 2016
- Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010
- Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
- Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
Adipic acid production from lignin
journal, January 2015
- Vardon, Derek R.; Franden, Mary Ann; Johnson, Christopher W.
- Energy & Environmental Science, Vol. 8, Issue 2
Sustainable polymers from renewable resources
journal, December 2016
- Zhu, Yunqing; Romain, Charles; Williams, Charlotte K.
- Nature, Vol. 540, Issue 7633
Production of Diethyl Terephthalate from Biomass-Derived Muconic Acid
journal, November 2015
- Lu, Rui; Lu, Fang; Chen, Jiazhi
- Angewandte Chemie, Vol. 128, Issue 1
Solvent effects in catalysis: rational improvements of catalysts via manipulation of solvent interactions
journal, January 2016
- Dyson, Paul J.; Jessop, Philip G.
- Catalysis Science & Technology, Vol. 6, Issue 10
Potential of Far-Ultraviolet Absorption Spectroscopy as a Highly Sensitive Quantitative and Qualitative Analysis Method for Aqueous Solutions, Part I: Determination of Hydrogen Chloride in Aqueous Solutions
journal, August 2004
- Higashi, Noboru; Ozaki, Yukihiro
- Applied Spectroscopy, Vol. 58, Issue 8
Molecular iodine-catalyzed one-pot synthesis of 4-substituted-1,4-dihydropyridine derivatives via Hantzsch reaction
journal, August 2005
- Ko, Shengkai; Sastry, M. N. V.; Lin, Chunchi
- Tetrahedron Letters, Vol. 46, Issue 34
Enhancing muconic acid production from glucose and lignin-derived aromatic compounds via increased protocatechuate decarboxylase activity
journal, December 2016
- Johnson, Christopher W.; Salvachúa, Davinia; Khanna, Payal
- Metabolic Engineering Communications, Vol. 3
Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds
journal, January 2017
- Settle, Amy E.; Berstis, Laura; Rorrer, Nicholas A.
- Green Chemistry, Vol. 19, Issue 15
Iodine catalyzed one-pot five-component reactions for direct synthesis of densely functionalized piperidines
journal, September 2010
- Khan, Abu T.; Khan, Md. Musawwer; Bannuru, Kranthi K. R.
- Tetrahedron, Vol. 66, Issue 39
Stress Corrosion Cracking of Titanium in Alcohol-Iodine Solutions
journal, May 1969
- Sedriks, A. J.
- CORROSION, Vol. 25, Issue 5
Environmentally compatible synthesis of adipic acid from D-glucose
journal, January 1994
- Draths, Karen M.; Frost, John W.
- Journal of the American Chemical Society, Vol. 116, Issue 1, p. 399-400
PROPHIS: parabolic trough-facility for organic photochemical syntheses in sunlight
journal, January 2005
- Jung, Christian; Funken, Karl-Heinz; Ortner, Jürgen
- Photochemical & Photobiological Sciences, Vol. 4, Issue 5
Visible Light Generation of Iodine Atoms and I−I Bonds: Sensitized I − Oxidation and I 3 − Photodissociation
journal, November 2009
- Gardner, James M.; Abrahamsson, Maria; Farnum, Byron H.
- Journal of the American Chemical Society, Vol. 131, Issue 44
Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar
journal, January 2016
- Suastegui, Miguel; Matthiesen, John E.; Carraher, Jack M.
- Angewandte Chemie, Vol. 128, Issue 7
Stress Corrosion Cracking and Corrosion Behavior of Ti and Ti-Al Alloys in Methanol Iodine Solutions
journal, June 1968
- Sedriks, A. J.; Green, J. A. S.; Slattery, P. W.
- CORROSION, Vol. 24, Issue 6
Parabolic-trough solar collectors and their applications
journal, September 2010
- Fernández-García, A.; Zarza, E.; Valenzuela, L.
- Renewable and Sustainable Energy Reviews, Vol. 14, Issue 7
Stress Corrosion Cracking of Zirconium and Zircaloy-4 in Iodine-Alcoholic Solutions
journal, May 2003
- Farina, S. B.; Duffó, G. S.; Galvele, J. R.
- CORROSION, Vol. 59, Issue 5
Iodine-Catalyzed Regioselective Sulfenylation of Indoles with Sulfonyl Hydrazides
journal, March 2013
- Yang, Fu-Lai; Tian, Shi-Kai
- Angewandte Chemie International Edition, Vol. 52, Issue 18
Molecular Iodine-Catalyzed Efficient and Highly Rapid Synthesis of Bis(indolyl)methanes under Mild Conditions.
journal, May 2003
- Bandgar, B. P.; Shaikh, K. A.
- ChemInform, Vol. 34, Issue 21
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