An efficient approach to produce 2,5‐diformylfuran from 5‐hydroxymethylfurfural using air as oxidant

Abstract

BACKGROUND 2,5‐Diformylfuran (DFF) is a versatile bio‐derived platform chemical. Multiple catalytic systems including homogeneous and heterogeneous catalysts have been studied for the oxidation of 5‐hydroxymethylfurfural (HMF) to DFF, but a more efficient and economical approach to produce DFF via HMF remains to be developed. RESULTS This study provides a practical approach to oxidizing HMF to DFF using Fe(NO3)3/Cu(NO3)2 as catalysts and air as oxidant with the assistance of K2S2O8. The typical oxidation of HMF to DFF was conducted under conditions of 4 wt% catalyst, 80 °C and 3 h, achieving an excellent DFF yield of over 99%. CONCLUSION In this oxidation reaction, Fe(NO3)3 played a crucial catalytic role by the redox cycle of Fe(III) and Fe(II), while Cu(NO3)2 functioned as a co‐catalyst to promote the redox cycle of Fe(II) and Fe(III) by the redox cycle of Cu(II) and Cu(I) with the assistance of oxygen. Meanwhile, NO2 released from the decomposition of Fe(NO3)3 during the redox cycle of Fe(II) and Fe(III) also participated in the oxidation of Fe(II) to Fe(III) by the redox cycle of NO2 and NO with the assistance of oxygen. Noteworthily, K2S2O8 provided an essential acidity to the oxidation of HMF to DFF through its decomposition product SO3. All these factors together ensured the efficient conversion of HMF and high selectivity of DFF. © 2019 Society of Chemical Industry

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO3/Cu(NO3)2 as Catalyst

“…One-pot synthesis of renewable phthalicanhydride from 5hydroxymethylfurfural On the basis of the previousp reparation of 2,5-diformylfuran (DFF) from HMF with Fe(NO 3 ) 3 /Cu(NO 3 ) 2 as catalyst,a99 % yield of DFF was obtained with the assistance of K 2 S 2 O 8 in acetonitrile. [22] On adding water to the reaction, PA was unexpectedly found in ay ield of 8%,a long with as ubstantial drop in the yield of DFF (Table1,e ntry 1). Spurred by this result, we soughtt oi dentify as uperior catalystt hat could increaset he conversion efficiency of HMF to PA by using K 2 S 2 O 8 as oxidant.…”

“…On the basis of the previous preparation of 2,5‐diformylfuran (DFF) from HMF with Fe(NO 3 ) 3 /Cu(NO 3 ) 2 as catalyst, a 99 % yield of DFF was obtained with the assistance of K 2 S 2 O 8 in acetonitrile . On adding water to the reaction, PA was unexpectedly found in a yield of 8 %, along with a substantial drop in the yield of DFF (Table , entry 1).…”

Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran by Visible Light‐Driven Photocatalysis over In Situ Substrate‐Sensitized Titania

“…DFF has a broad range of potential applications as an intermediate for the synthesis of macrocyclic ligands, bio‐based polymeric materials, pharmaceutical products, or antifungal agents etc [7] . Consequently, the selective oxidation of HMF to DFF has received considerable attention to date [8–10] …”

Hydroxyapatite‐Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural or Glucose to 2,5‐Diformylfuran under Atmospheric Pressure

“…There was few reports on 5-HMF oxidation upon oxygen under atmospheric pressure or upon air so far. [22][23][24][25][26] Thus, a new catalytic system is required to be developed to achieve 5-HMF oxidation to DFF under atmospheric pressure with high efficiency. Additionally, the one-pot conversion of monosaccharides (such as fructose and glucose) into DFF is of greater value and lower cost in comparison to production of DFF from 5-HMF.…”

“…In the present study, we developed a new approach to preparing POM ((NH 4 ) 5 H 6 PV 8 Mo 4 O 40 ) doped in HAP and investigated their catalytic performance in 5‐HMF cascade conversion into DFF. DFF is generally produced from the transformation of 5‐HMF with a high yield of more than 90 % by homogeneous or heterogeneous catalysts (Table S1, Supporting Information) [10,21–49] . Among reported catalysts, POMs containing V and Mo were proved to be active in targeted aerobic oxidation of 5‐HMF to DFF [42,50] .…”