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Angew Chem Int Ed Engl. 2016 Jan 4;55(1):249-53. doi: 10.1002/anie.201509149. Epub 2015 Nov 23.

Production of Diethyl Terephthalate from Biomass-Derived Muconic Acid.

Lu R1,2, Lu F3, Chen J1,2, Yu W1, Huang Q1,2, Zhang J1,2, Xu J4.

Author information

1
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023 (PR China) http://www.orgcatal.dicp.ac.cn.
2
University of Chinese Academy of Sciences, Beijing 100049 (PR China).
3
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023 (PR China) http://www.orgcatal.dicp.ac.cn. lufang@dicp.ac.cn.
4
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, 457 Zhongshan Road, Dalian 116023 (PR China) http://www.orgcatal.dicp.ac.cn. xujie@dicp.ac.cn.

Abstract

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.

KEYWORDS:

biomass; catalysis; cycloaddition; muconic acid; terephthalic acid

PMID:
26592149
DOI:
10.1002/anie.201509149

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