Electrolysis is a sustainable synthetic strategy that uses electric current or potential to drive reactions (opposed to conventional reagent-driven synthesis). While electrolysis can be both energy-efficient and reduce reagent waste, it can also be difficult to develop conditions that produce the desired reaction. Since electrolysis works by directly applying energy, synthetic procedures using this technique may lack selectivity control, be vulnerable to over-reaction, and be limited due to electrode surface area and electrolyte circulation. 5-hydroxymethylfurfural (HMF) can be oxidized to 2,5-diformylfuran (DFF), a valuable carbaldehyde product. DFF is used for the synthesis of pharmaceutical, agrochemical, and polymer precursors, such as the primary diamine 2,5-Bis(aminomethyl)furan (BAMF). This work examines the electrochemical oxidation of HMF to DFF—performed in a dual-chamber cell using a LiClO4/acetonitrile electrolyte solution—and compares it to the conventional chemical oxidation. Compared to the electrochemical oxidation, the chemical oxidation shows better yield and purity, based on respective 1H-NMR spectra. However, the chemical oxidation procedure was a successful replication of a published procedure, which helps account for discrepancies in yield and purity between both methods. While the electrochemical procedure was measurably less effective, successful improvement over the course of experimental testing indicates that further fine-tuning will increase effectiveness. In order to properly utilize electrolysis for the sustainable oxidation of HMF to DFF, the reaction conditions must be optimized to increase yield to a level that rivals the conventional synthesis. Since this oxidation is the first step in the synthesis of other value-added products such as BAMF, future work should also include generating an electrochemical procedure for the reduction of DFF that uses similar conditions. The ultimate goal will be to set up a flow cell for successive electrochemical reactions, that can use the same current simultaneously without the need to isolate products between steps, therefore minimizing waste on multiple levels.

Comparing chemical vs. electrochemical oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

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