Oxidation of Furfural and Furan Derivatives to Maleic Acid in the Presence of a Simple Catalyst System Based on Acetic Acid and TS-1 and Hydrogen Peroxide

Abstract

Titanium silicate molecular sieve (TS-1) and acetic acid efficiently catalyze the oxidation of furan and furan derivatives to the corresponding maleic acid (MA) in very good yields using hydrogen peroxide as an oxidizing agent. The effect of various solvents, the effect of temperature, reaction time, concentration of hydrogen peroxide, and quantities of the catalyst on the MA yield was studied. With the best conditions, MA is the sole product obtained after a fast and simple purification by filtration and evaporation. Compared to the previously reported methods, this work is a good compromise between the different reaction parameters and offers a good alternative to the production of biosourced MA.

Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

“…The excellent solubility of protoanemonin and 5‐(hydroxymethyl)furfural ( 1 ) in chlorinated solvents and the high conversion in reduced reaction times, allowed us to confirm the noteworthy stabilization of performic acid, the active oxidizing agent, which is generated in situ from formic acid [3b] . This peroxy acid could be transferred from the aqueous phase of hydrogen peroxide to the organic phase of chlorinated solvent, improving the interaction with the substrates in the same phase.…”

“…One interesting aspect is the increasing in formic and acetic acids during the course of the reaction (0.5 to 8 h), whose presence drastically decreased after 24 h of reaction. This is clear evidence that oxidation processes are accompanied by the autocatalysis of those acids, which may form in situ performic and peracetic acids, [3b,18] key intermediates to catalyse these oxidation processes.…”

“…The use of hydrogen peroxide has the advantage of forming distinct reactive species (singlet and triplet oxygen, hydroxyl and perhydroxyl ions and radicals) depending on the decomposition conditions, [2] and the reactions between furans could be manipulated based on the reaction conditions. Overall, the oxidation of furfural to produce dicarboxylic acids has been extensively studied; [3] the yields depend on the type of substituent on the furan ring, [3a,b] reaction temperature, and the amount of oxidant agent employed [3d] . It is importat to note that diverse transformations of HMF into DFF, anhydride maleic, and maleic acid are conducted with vanadium‐based catalysts under molecular oxygen atmosphere [4] .…”

Selective Oxidation of Furfural to 2(5H)-Furanone and Maleic Acid over CuMoO4

“…By comparison, the heterogeneous oxidation of furfural with O 2 is more promising due to the advantage of catalyst recovery and a green oxidant. Although a great deal of research has been conducted for the oxidation of furfural to MAc by heterogeneous catalysts in the recent decade, the yield of MAc is still at a moderate level ranging from 37 to 78%. , …”

“…Although a great deal of research has been conducted for the oxidation of furfural to MAc by heterogeneous catalysts in the recent decade, the yield of MAc is still at a moderate level ranging from 37 to 78%. 32,33 Recently, Lan et al 34 applied H 5 PV 2 Mo 10 O 40 and Cu-(CF 3 SO 3 ) 2 as catalysts for catalytic oxidation of furfural, which provided a high yield (54%) of maleic anhydride. Meanwhile, 7.5% yield of furanone derivatives was also detected.…”