Efficient Syntheses of Biobased Terephthalic Acid, p-Toluic Acid, and p-Methylacetophenone via One-Pot Catalytic Aerobic Oxidation of Monoterpene Derived Bio-p-cymene.
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Publication Date
2021-06-28Journal Title
ACS Sustain Chem Eng
ISSN
2168-0485
Publisher
American Chemical Society (ACS)
Volume
9
Issue
25
Pages
8642-8652
Language
eng
Type
Article
This Version
VoR
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Tibbetts, J. D., Russo, D., Lapkin, A. A., & Bull, S. D. (2021). Efficient Syntheses of Biobased Terephthalic Acid, p-Toluic Acid, and p-Methylacetophenone via One-Pot Catalytic Aerobic Oxidation of Monoterpene Derived Bio-p-cymene.. ACS Sustain Chem Eng, 9 (25), 8642-8652. https://doi.org/10.1021/acssuschemeng.1c02605
Abstract
An efficient elevated-pressure catalytic oxidative process (2.5 mol % Co(NO3)2, 2.5 mol % MnBr2, air (30 bar), 125 °C, acetic acid, 6 h) has been developed to oxidize p-cymene into crystalline white terephthalic acid (TA) in ∼70% yield. Use of this mixed Co2+/Mn2+ catalytic system is key to obtaining high 70% yields of TA at relatively low reaction temperatures (125 °C) in short reaction times (6 h), which is likely to be due to the synergistic action of bromine and nitrate radicals in the oxidative process. Recycling studies have demonstrated that the mixed metal catalysts present in recovered mother liquors could be recycled three times in successive p-cymene oxidation reactions with no loss in catalytic activity or TA yield. Partial oxidation of p-cymene to give p-methylacetophenone (p-MA) in 55-60% yield can be achieved using a mixed CoBr2/Mn(OAc)2 catalytic system under 1 atm air for 24 h, while use of Co(NO3)2/MnBr2 under 1 atm O2 for 24 h gave p-toluic acid in 55-60% yield. Therefore, access to these simple catalytic aerobic conditions enables multiple biorenewable bulk terpene feedstocks (e.g., crude sulfate turpentine, turpentine, cineole, and limonene) to be converted into synthetically useful bio-p-MA, bio-p-toluic acid, and bio-TA (and hence bio-polyethylene terephthalate) as part of a terpene based biorefinery.
Sponsorship
Engineering and Physical Sciences Research Council (EP/K014889/1)
Engineering and Physical Sciences Research Council (EP/R009902/1)
Identifiers
PMC8735764, 35024250
External DOI: https://doi.org/10.1021/acssuschemeng.1c02605
This record's URL: https://www.repository.cam.ac.uk/handle/1810/333981
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