Brønsted Acid Catalyzed Tandem Defunctionalization of Biorenewable Ferulic acid and Derivates into Bio‐Catechol

• Published in: Angewandte Chemie International Edition Vol. 59; no. 8; pp. 3063 - 3068
• Main Authors: Bomon, Jeroen, Van Den Broeck, Elias, Bal, Mathias, Liao, Yuhe, Sergeyev, Sergey, Van Speybroeck, Veronique, Sels, Bert F., Maes, Bert U. W.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 17.02.2020; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Acids; bond cleavage; C-dealkylation; Catalysts; Catechol; Chemistry; Chemistry, Multidisciplinary; Demethylation; Ferulic acid; green chemistry; Hydroquinone; O-dealkylation; Physical Sciences; Pyrogallol; renewable resources; Resorcinol; Science & Technology; Substrates; Sulfuric acid; C-dealkylation; renewable resources; ALKYLAROMATIC COMPOUNDS; PHENOL; bond cleavage; CONVERSION; IONIC LIQUID; MODEL COMPOUNDS; CLEAVAGE; green chemistry; O-dealkylation; LIGNIN DEPOLYMERIZATION; KINETICS; SHAPE SELECTIVITY; DEALKYLATION
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201913023

An efficient conversion of biorenewable ferulic acid into bio‐catechol has been developed. The transformation comprises two consecutive defunctionalizations of the substrate, that is, C−O (demethylation) and C−C (de‐2‐carboxyvinylation) bond cleavage, occurring in one step. The process only requires heating of ferulic acid with HCl (or H2SO4) as catalyst in pressurized hot water (250 °C, 50 bar N2). The versatility is shown on a variety of other (biorenewable) substrates yielding up to 84 % di‐ (catechol, resorcinol, hydroquinone) and trihydroxybenzenes (pyrogallol, hydroxyquinol), in most cases just requiring simple extraction as work‐up. Ferulic acid, a bio‐renewable compound derived from rice bran, has been transformed in catechol, a major commodity chemical, using HCl and water. The protocol is applicable to a variety of other (biorenewable) substrates.