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Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Pacheco, Joshua J. and Davis, Mark E. (2014) Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural. Proceedings of the National Academy of Sciences of the United States of America, 111 (23). pp. 8363-8367. ISSN 0027-8424. PMCID PMC4060660. doi:10.1073/pnas.1408345111. https://resolver.caltech.edu/CaltechAUTHORS:20140602-151610855

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Abstract

Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1073/pnas.1408345111 DOIArticle
http://www.pnas.org/content/111/23/8363PublisherArticle
http://www.pnas.org/lookup/suppl/doi:10.1073/pnas.1408345111/-/DCSupplementalPublisherSupporting Information
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4060660/PubMed CentralArticle
ORCID:
AuthorORCID
Davis, Mark E.0000-0001-8294-1477
Additional Information:© 2014 National Academy of Sciences. Freely available online through the PNAS open access option. Contributed by Mark E. Davis, May 7, 2014 (sent for review April 16, 2014). Published ahead of print May 27, 2014. This work was funded by Toray Industries. Author contributions: J.J.P. and M.E.D. designed research; J.J.P. performed research; J.J.P. and M.E.D. analyzed data; and J.J.P. and M.E.D. wrote the paper. The authors declare no conflict of interest. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1408345111/-/DCSupplemental.
Funders:
Funding AgencyGrant Number
Toray IndustriesUNSPECIFIED
Issue or Number:23
PubMed Central ID:PMC4060660
DOI:10.1073/pnas.1408345111
Record Number:CaltechAUTHORS:20140602-151610855
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140602-151610855
Official Citation:Joshua J. Pacheco and Mark E. Davis Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural PNAS 2014 111 (23) 8363-8367; published ahead of print May 27, 2014, doi:10.1073/pnas.1408345111
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:46035
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Jun 2014 22:55
Last Modified:10 Nov 2021 17:19

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