A gram scale selective oxidation of 5-hydroxymethylfurfural to diformylfuran in the presence of oxone and catalyzed by 2-iodobenzenesulfonic acid

Abstract

In the present work, an alternative system of 5-hydroxymethylfurfural (HMF) oxidation was studied, in an attempt to avoid the use of expensive metal catalysts, polluting systems and high pressures.

Metal vs. Metal‐Free Catalysts for Oxidation of 5‐Hydroxymethylfurfural and Levoglucosenone to Biosourced Chemicals

“…Interestingly, this method could be extended to a gram-scale production of DFF without any effect on the selectivity. [161] Among the hypervalent iodine derivatives we have seen previously that [bis(acetoxy)-iodo] benzene has also been used with interest as a co-oxidant in combination with TEMPO for the selective oxidation of HMF to DFF. Under these mild conditions 66 and 73 % DFF yield are obtained selectively in the presence of low proportions of TEMPO.…”

“…Acid catalysts like Amberlyst-15 and IBS afforded great conversion and yield with the possibility to scale up the process to gram scale. [161] Moreover, carbon based catalysts; especially GO with TEMPO, provided total conversion with more than 99 % DFF yield. [122] In general, following the different classes of metal-free catalysts, we observe that oxidizing acid catalysis with nitric acid leads to FDCA but with lower yields of the order of 11 to 67 %, whereas in the case of metal catalysis yields of 80-100 % are frequently reported.…”

“…Under optimal conditions, DFF yield was 89 % with total conversion of HMF (Table 6, entry 1) with high grade of purity using IBS catalyst and Oxone as co‐oxidant. Interestingly, this method could be extended to a gram‐scale production of DFF without any effect on the selectivity [161] . Among the hypervalent iodine derivatives we have seen previously that [bis(acetoxy)‐iodo] benzene has also been used with interest as a co‐oxidant in combination with TEMPO for the selective oxidation of HMF to DFF.…”

“…With these catalysts, oxidation selectivity over the hydroxy group is frequently well controlled. Acid catalysts like Amberlyst‐15 and IBS afforded great conversion and yield with the possibility to scale up the process to gram scale [161] . Moreover, carbon based catalysts; especially GO with TEMPO, provided total conversion with more than 99 % DFF yield [122] …”

Aerobic oxidation of aldehydes to acids in water with cyclic (alkyl)(amino)carbene copper under mild conditions

“…1 In particular, oxidation of aldehydes to give organic acids is one of the well-known and potential technologies in the field of chemical engineering. [2][3][4] It has long been known that a wide range of unfavorable oxidants, including potassium permanganate, 5 periodate, 6 oxone, 7 and chromium trioxide, 8 were utilized to realize this process. However, they suffer from considerable disadvantages such as high cost, inefficient performance, and hazardous environmental issues.…”