Efficient Syntheses of Biobased Terephthalic Acid, p-Toluic Acid and p-Methylacetophenone via One-Pot Catalytic Aerobic Oxidation of Monoterpene Derived bio-p-Cymene

Joshua D. Tibbetts, Danilo Russo, Alexei Lapkin, Steven D. Bull

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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 ∼0% 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.

Original languageEnglish
Pages (from-to)8642–8652
JournalACS Sustainable Chemistry and Engineering
Volume9
Issue number25
Early online date17 Jun 2021
DOIs
Publication statusPublished - 28 Jun 2021

Keywords

  • Bio- p-cymene
  • Bio- p-methylacetophenone
  • Bio- p-toluic acid
  • Bio-terephthalic acid
  • Catalytic aerobic oxidation
  • Terpene biorefinery

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Chemical Engineering(all)
  • Renewable Energy, Sustainability and the Environment

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