Iodine-Catalyzed Isomerization of Dimethyl Muconate

Amy E. Settle, Laura Berstis, Shuting Zhang, Nicholas A. Rorrer, Haiming Hu, Ryan M. Richards, Gregg T. Beckham, Michael F. Crowley, Derek R. Vardon

Research output: Contribution to journalArticlepeer-review

17 Scopus Citations

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 (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 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, 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. 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.

Original languageAmerican English
Pages (from-to)1768-1780
Number of pages13
JournalChemSusChem
Volume11
Issue number11
DOIs
StatePublished - 2018

Bibliographical note

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

NREL Publication Number

  • NREL/JA-5100-71487

Keywords

  • biomass upgrading
  • density functional theory
  • iodine
  • muconic acid
  • reaction mechanism

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