Diels-Alder and Dehydration Reactions of Biomass-Derived Furan and Acrylic Acid for the Synthesis of Benzoic Acid

Eyas Mahmoud, Jingye Yu, Raymond J. Gorte, Raul F. Lobo

Research output: Contribution to journalArticlepeer-review

71 Citations (Scopus)

Abstract

Routes to benzoic acid starting from furan-obtained from hemicellulose in high yield-and methyl acrylate are reported. These routes involve Diels-Alder and dehydration reactions of furan and acrylic acid (or methyl acrylate) in a two-step reaction protocol that minimizes side reactions. The Diels-Alder reaction of furan and methyl acrylate (or acrylic acid) was run at 298 K and was catalyzed by Lewis acidic (Hf-, Zr-, and Sn-Beta) zeolite catalysts, and achieving a high turnover frequency (∼2 h-1) and no side reactions were observed. The oxanorbornene product was dehydrated at low temperatures (298 to 353 K) in mixtures of methanesulfonic acid and acetic anhydride in 96% yield. This is compared to an only 1.7% yield of methyl benzoate obtained for the dehydration of the oxanorbornene in neat methanesulfonic acid. The effect of oxanorbornene concentration and stereochemistry was found not to decrease the yield of aromatics, while dehydration of the carboxylic acid form of the oxanorbornene led to a decrease in selectivity to 43% at complete conversion in mixtures of methanesulfonic acid and acetic anhydride. This reaction sequence could be an important entry point for selectively directing high-yield, hemicellulose-derived furans to aromatic products used in the existing chemical process industry.

Original languageEnglish
Pages (from-to)6946-6955
Number of pages10
JournalACS Catalysis
Volume5
Issue number11
DOIs
Publication statusPublished - Nov 6 2015
Externally publishedYes

Keywords

  • Diels-Alder
  • Lewis acid
  • dehydration
  • mixed anhydrides
  • zeolite Beta

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Fingerprint

Dive into the research topics of 'Diels-Alder and Dehydration Reactions of Biomass-Derived Furan and Acrylic Acid for the Synthesis of Benzoic Acid'. Together they form a unique fingerprint.

Cite this