Selective sodium chlorite oxidations in aqueous solution with sulfamic acid and biomass-derived platform chemicals—such as 5-hydroxymethylfurfural (HMF) or 2,5-dimformylfuran (DFF)—have provided ready access to a range of challenging and valuable carboxylic acid platform chemicals in high yield. Recently, our group has improved the efficiency and lowered the environmental impact of biomass-derived dialdehyde feedstock preparation. For example, the halogenated solvent (dichloromethane) was replaced and the amount of oxidant was reduced in the selective oxidation of HMF into DFF in ethyl acetate solution with manganese dioxide. While developing coatings applications based on those dialdehydes we became interested in the aromatic aldehydes readily accessible from cellulosic biorefinery as intermediates in the synthesis of renewable terephthalic acid analogs By adapting the conditions of Lindgren and Nilsson, we have achieved greater access to designer diacids for polymer synthesis and other applications. The now readily accessible platform chemicals, 5-hydroxymethylfuroic acid (HMFA) and 5-formylfuroic acid (FFA) have provided the opportunity to synthesize a series of even and oddly spaced rigid diacid building blocks with a variety of linkages by dehydrative etherification, and Knoevenagel condensation. Reaction optimizations were informed by the principles of green chemistry and comparisons of multiple methods in terms of atom economy and complete e-factor will be presented.

Green oxidation of biomass-derived feedstocks with sodium chlorite/sulfamic acid

256th National Meeting (2018)

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