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H 2 ‐Free Re‐Based Catalytic Dehydroxylation of Aldaric Acid to Muconic and Adipic Acid Esters
Author(s) -
Hočevar Brigita,
Prašnikar Anže,
Huš Matej,
Grilc Miha,
Likozar Blaž
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202010035
Subject(s) - adipic acid , muconic acid , chemistry , catalysis , yield (engineering) , organic chemistry , mineral acid , valeric acid , inert gas , solid acid , cellulose , adipate , cyclohexanol , cyclohexane , polymer chemistry , acetic acid , benzene , aqueous solution , materials science , metallurgy
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 °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.