H2-Free Re-Based Catalytic Dehydroxylation of Aldaric Acid to Muconic and Adipic Acid Esters

As one of the most demanded dicarboxylic acids, adipic acid can be directly produced from renewable sources. Hexoses from (hemi)cellulose are oxidized to aldaric acids and subsequently catalytically dehydroxylated. Hitherto performed homogeneously, we present the first heterogeneous catalytic process for converting an aldaric acid into muconic and adipic acid. The contribution of leached Re from the solid pre-reduced catalyst was also investigated with hot-filtration test and found to be inactive for dehydroxylation. Corrosive or hazardous (HBr/H-2) reagents are avoided and simple alcohols and solid Re/C catalysts in an inert atmosphere are used. At 120 degrees C, the carboxylic groups are protected by esterification, which prevents lactonization in the absence of water or acidic sites. Dehydroxylation and partial hydrogenation yield monohexenoates (93 %). For complete hydrogenation to adipate, a 16 % higher activation barrier necessitates higher temperatures.

Automated summary

This study presents the first heterogeneous catalytic process for converting aldaric acid into muconic and adipic acid, using simple alcohols and solid Re/C catalysts in an inert atmosphere. The use of corrosive or hazardous reagents is avoided, with a focus on producing adipic acid directly from renewable sources.