Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural

Abstract

A new method was developed for the selective gram-scale synthesis of 2,5-diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass-derived 5-hydroxylmethylfurfural (HMF) catalyzed by 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-AcNH-TEMPO) in a two-phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I2 (co-)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62-65 % yield of DFF. This novel method provides a sustainable pathway for waste-free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.

Photoelectrochemical hybrid cell for unbiased CO2 reduction coupled to alcohol oxidation

“…HPLC analysis revealed a selectivity for DFF, a high-value monomer employed in the polymer industry 8 , with no overoxidation products being detected. This may be a consequence of the low overall conversion yield (Supplementary Table 11) and of the experimental conditions, which can impact product selectivity 50,51 . DFF was produced with a FE of 86−90% under both electrolyte conditions (Supplementary Table 11).…”

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions

“…Ananikov and co-workers later reported the electrooxidation of HMF to 2,5-diformylfuran (DFF) in a two-phase solution, with ACT and iodide as a double-mediator system (Scheme 59). 155 DFF is a monomer and a building block for polymer and pharmaceutical applications, but selective oxidation of HMF to DFF is challenging due to the oxidatively sensitive formyl groups present in both HMF and DFF. For the TEMPO-mediated method, however, DFF was obtained in 61−63% yields.…”

Simultaneous analysis of 2‐methylimidazole, 4‐methylimidazole, and 5‐hydroxymethylfurfural potentially formed in fermented soy sauce by “quick, easy, cheap, effective, rugged, and safe” purification and UHPLC with tandem mass spectrometry

“…Therefore, effective extraction and favorable purification of complex matrix play vital roles in the pretreatment and the following instrument detection. Diatomite column and dichloromethane have been commonly used for the extraction of MID and 5‐HMF in liquid seasoning . However, cumbersome operation, poor reproducibility and high LOD constrain their broad applications.…”