Highly efficient formic acid-mediated oxidation of renewable furfural to maleic acid with H₂O₂

Abstract

Maleic acid is produced from biomass-derived furfural or 5-hydroxymethylfurfural under metal catalyst-free conditions employing H2O2 as an oxidant in formic acid.

Metal Catalyst‐Free Oxidative C−C Bond Cleavage of a Lignin Model Compound by H2O2 in Formic acid

“…With increasing length of the carbon chain, the acidity of the organic acid decreases and the dissociation of the intermediate becomes slower (see Table ). Similar effects of the organic acid on the BVO were also observed in our previous study on furfural oxidation to maleic acid by H 2 O 2 . Using in situ‐generated organic peracids as oxidants is a method for biomass valorization, but the extent of oxidations and the product selectivities are strongly dependent on the type and concentration of the organic acid employed in the reaction …”

“…The dissociation of 2 leads to benzoic acid 3 and phenol 4 . Organic peracids have stronger O−O bonds than H 2 O 2 because of the electron‐withdrawing effect of the carbonyl group . Moreover, organic acids and peracids provide strong acidic environments that are favorable for the BVO and the dissociation of the intermediate product 2 .…”

“…Based on the results of kinetic study and NMR spectroscopy,w epropose the reaction should follow ac lassic Baeyer-Villiger oxidation mechanism (Scheme 2), whereby performic acid attacks the carbonyl group of 1 to form the Criegee intermediate, which is then convertedi nto acetal ester 2.T he dissociation of 2 leads to benzoica cid 3 and phenol 4.O rganic peracidsh ave stronger OÀOb onds than H 2 O 2 because of the electron-withdrawing effect of the carbonylg roup. [13] Moreover,o rganic acidsa nd peracids provide stronga cidic environments that are favorable fort he BVO and the dissociation of the intermediate product 2.W ithi ncreasingl ength of the carbon chain, the acidity of the organic acid decreasesa nd the dissociation of the intermediate becomess lower (see Ta ble 1). Similar effects of the organic acid on the BVO were also observed in our previous study on furfu- [13] Using in situ-generated organic peracids as oxidants is am ethod for biomass valorization, but the extent of oxidations and the product selectivities are strongly dependent on the type and concentration of the organic acide mployedi nt he reaction.…”

“…[13] Moreover,o rganic acidsa nd peracids provide stronga cidic environments that are favorable fort he BVO and the dissociation of the intermediate product 2.W ithi ncreasingl ength of the carbon chain, the acidity of the organic acid decreasesa nd the dissociation of the intermediate becomess lower (see Ta ble 1). Similar effects of the organic acid on the BVO were also observed in our previous study on furfu- [13] Using in situ-generated organic peracids as oxidants is am ethod for biomass valorization, but the extent of oxidations and the product selectivities are strongly dependent on the type and concentration of the organic acide mployedi nt he reaction. [13,14] The reactionc onducted at room temperaturew ould be energy efficient.…”

Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran or 2‐Formyl‐5‐furancarboxylic Acid in Water by using MgO⋅CeO2 Mixed Oxides as Catalysts

“…[17] Studies of catalytic systems based of N-hydroxyphthalimide with ceria showedt hat increasing the amount of ceria produces differentr esults. [18] Au [19] and Cr [20] were also tested, but led to no more than 30 %s electivity.A lthough the synthesis of FDCA with excellent yield and selectivity has recently been reported, [21] good yields or selectivities for DFF,w hich is an intermediate in FDCA synthesis (Scheme 2), is still am atter of research. [18] Au [19] and Cr [20] were also tested, but led to no more than 30 %s electivity.A lthough the synthesis of FDCA with excellent yield and selectivity has recently been reported, [21] good yields or selectivities for DFF,w hich is an intermediate in FDCA synthesis (Scheme 2), is still am atter of research.…”