2205-27-8Relevant academic research and scientific papers
Cis, cis -Muconic acid isomerization and catalytic conversion to biobased cyclic-C6-1,4-diacid monomers
Carraher, Jack M.,Pfennig, Toni,Rao, Radhika G.,Shanks, Brent H.,Tessonnier, Jean-Philippe
, p. 3042 - 3050 (2017)
Renewable terephthalic and 1,4-cyclohexanedicarboxylic acids can be produced from biomass via muconic acid using a combination of biological and chemical processes. In this conversion scheme, cis,cis-mucononic acid is first obtained by fermentation using
Solvent-driven isomerization of: cis, cis -muconic acid for the production of specialty and performance-advantaged cyclic biobased monomers
Carraher, Jack M.,Carter, Prerana,Cochran, Eric W.,Forrester, Michael J.,Pfennig, Toni,Rao, Radhika G.,Shanks, Brent H.,Tessonnier, Jean-Philippe
, p. 6444 - 6454 (2020)
The quest for green plastics calls for new routes to aromatic monomers using biomass as a feedstock. Suitable feedstock molecules and conversion pathways have already been identified for several commodity aromatics through retrosynthetic analysis. However, this approach suffers from some limitations as it targets a single molecule at a time. A more impactful approach would be to target bioprivileged molecules that are intermediates to an array of commodity and specialty chemicals along with novel compounds. Muconic acid (MA) has recently been identified as a bioprivileged intermediate as it gives access to valuable aliphatic and cyclic diacid monomers including terephthalic acid (TPA), 1,4-cyclohexanedicarboxylic acid (CHDA), and novel monounsaturated 1,4-cyclohexenedicarboxylic acids (CH1DA, CH2DA). However, accessing these cyclic monomers from MA requires to first isomerize biologically-produced cis,cis-MA to Diels-Alder active trans,trans-MA. A major impediment in this isomerization is the irreversible ring closing of MA to produce lactones. Herein, we demonstrate a green solvent-mediated isomerization using dimethyl sulfoxide and water. The mechanistic understanding achieved here elucidates the role of low concentrations of water in reducing the acidity of the system, thereby preventing the formation of lactones and improving the selectivity to trans,trans-MA from less than 5% to over 85%. Finally, a Diels-Alder reaction with trans,trans-MA is demonstrated with ethylene. The monounsaturated cyclic diacid obtained through this reaction (CH1DA) can be converted in a single step into TPA and CHDA, or can be directly copolymerized with adipic acid and hexamethylenediamine to tailor the thermal and mechanical properties of conventional Nylon 6,6.
Production of Diethyl Terephthalate from Biomass-Derived Muconic Acid
Lu, Rui,Lu, Fang,Chen, Jiazhi,Yu, Weiqiang,Huang, Qianqian,Zhang, Junjie,Xu, Jie
supporting information, p. 249 - 253 (2016/01/25)
We report a cascade synthetic route to directly obtain diethyl terephthalate, a replacement for terephthalic acid, from biomass-derived muconic acid, ethanol, and ethylene. The process involves two steps: First, a substituted cyclohexene system is built through esterification and Diels-Alder reaction; then, a dehydrogenation reaction provides diethyl terephthalate. The key esterification reaction leads to improved solubility and modulates the electronic properties of muconic acid, thus promoting the Diels-Alder reaction with ethylene. With silicotungstic acid as the catalyst, nearly 100 % conversion of muconic acid was achieved, and the cycloadducts were formed with more than 99.0 % selectivity. The palladium-catalyzed dehydrogenation reaction preferentially occurs under neutral or mildly basic conditions. The total yield of diethyl terephthalate reached 80.6 % based on the amount of muconic acid used in the two-step synthetic process.
PREPARATION OF TRANS,TRANS MUCONIC ACID AND TRANS,TRANS MUCONATES
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Page/Page column 26, (2010/12/29)
The present invention relates to the isomerization of cis,cis and/or cis,trans muconic acid or esters thereof to trans,trans muconic acid or esters thereof and to the esterification of such muconic acids.
