The shift from fossil to biomass-derived fuels is dependent on proving the utility of the various components of renewable biomass. Therefore, research geared toward increasing the value of biomass involves identifying specific uses of these components, thus increasing the overall profitability of biomass production. As solvents can account for up to 80% of the mass of batch, chemical processes, biomass derived solvents are of keen importance in this necessary transition towards more sustainable manufacturing. N-Arylation is one of the most useful reactions in medicinal chemistry,<sup> </sup>agrochemistry, and in material sciences. Currently, one of the more common methods of this synthesis is through the Ullmann-type reaction. Such copper-based methods offer the advantages of reduced price and toxicity, but require additional ligands at higher loadings, harsher conditions and high-boiling point solvents. Although much progress has been made with this reaction, the challenge remains to develop a less expensive and more sustainable process. Biomass derived furfuryl alcohol (FA) owns the properties of being soluble in common organic solvents, miscible in water, and of stabilizing copper-complexes. Previous research from this group showed that pure FA can form an azeotrope with water (20 wt% of FA) that boils at a lower temperature, reasonable for distillation. The use of this FA azeotrope as reaction media is here examined in Ullmann-type, copper catalyzed, cross coupling amination reactions. The protocol developed shows the successful use of this azeotrope as reaction media as well as the ability to avoid the use of further ligands or additive. This mixture has also been shown to be recoverable and reusable in at least two subsequent reactions. The procedure developed here allowed for easy isolation, in good to excellent yields, with low waste production.

Biomass derived furfuryl alcohol/water azeotrope as reaction medium for copper-catalyzed Ullmann-type condensation

253rd National Meeting (2017)

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