Biomass-Derived, Target Specific, and Ecologically Safer Insecticide Active Ingredients.

With the continuous increase in food production to support the growing population, ensuring agricultural sustainability using crop-protecting agents, such as pesticides, is vital. Conventional pesticides pose significant environmental risks, prompting the need for eco-friendly alternatives. This study reports the synthesis of new amide-based insecticidal active ingredients from biomass-derived monomers, specifically furfural and vanillin. The process involves reductive amination followed by carbonylation. The synthesis of the furfural-based carbamate yield reaches a cumulative 88 %, with catalysts Rh/Al2O3 and La(OTf)3 being recyclable at each stage. Insecticidal activity assessments reveal that the furfural carbamate exhibits competitive performance, achieving an LC50 of 254.22 µg/cm2, compared to 251.25 µg/cm2 for carbofuran. Ecotoxicity predictions indicate significantly lower toxicity levels toward non-target aquatic and terrestrial species. The importance of the low octanol-water partition coefficient of the biobased carbamate, attributed to the oxygen heteroatom and electron density of the furan ring, is discussed in detail. Building on these promising results, the synthesis strategy was extended to six other biobased aldehydes, resulting in a diverse portfolio of biomass-derived carbamates. A techno-economic analysis reveals a minimum selling price of 11.1 $/kg, only half that of comparable carbamates, demonstrating the economic viability of these new biobased insecticides.

Synthesis of Long Chain Oxygenates via Aldol Condensation of Furfural and Acetone over Metal-Organic Frameworks.

Enormous efforts have been made to convert biomass to liquid fuels and products catalytically. Long molecules with a suitable structure are ideal precursors for fuels and value-added products. Here, a C21 oxygenate was synthesized for the first time in one step through aldol condensation of furfural and acetone over the amine-functionalized zirconium-based metal-organic framework (MOF), UiO-66-NH2. Structural changes of UiO-66-NH2 were investigated to improve the yield and evaluate the role of the ligand, cluster node, defectiveness, modulator, surface area, and textural properties on the product distribution. We demonstrate the possibility of making long-chain oxygenates without using vegetable oil-derived fatty acids toward 100% waste biomass-derived renewable fuels, lubricants, and surfactants.