Chitin and Silk Fibroin Biopolymers Modified by Oxone: Efficient Heterogeneous Catalysts for Knoevenagel Reaction

Abstract

New materials from silk fibroin (FS-Ox) and chitin (CT-Ox) functionalized with Oxone® salt were developed for application in the synthesis of Knoevenagel adducts. The experiments were performed using benzaldehyde derivatives, malononitrile, and a mixture of water and ethanol as green solvents. The efficiency of conventional and microwave irradiation as heating sources for this reaction was also investigated. When the reactions were performed for 60 min under optimized conditions with conventional heating, twelve Knoevenagel adducts 2a–l were obtained, with good yields for both catalysts (CT-Ox 60–98% and FS-Ox 71–98%). When microwave irradiation was used, the reaction periods were reduced twelvefold, with the same Knoevenagel adducts with good CT-Ox (39–99%) and FS-Ox (35–99%) yields obtained in most cases. The reuse of these materials as catalysts in successive reactions was also evaluated, and CT-Ox FS-Ox were successfully used for 4 and 2 cycles, respectively. The results presented prove the efficiency of the CT-OxFS-Ox catalyst as a promising low-cost and reusable material with suitable catalytic properties to be applied in the aldol condensation reaction in a sustainable way.