A post-sulfonated one-pot synthesized magnetic cellulose nanocomposite for Knoevenagel and Thorpe-Ziegler reactions

The development of biodegradable and active cellulosic-based heterogeneous catalysts for the synthesis of different organic compounds would be attractive in pharmaceutical and petrochemical-related industries. Herein, a post-sulfonated composite of one-pot synthesized magnetite (Fe₃O₄) and cellulose nanocrystals (CNCs) was used as an effective and easily separable heterogeneous catalyst for activating the Knoevenagel and Thorpe-Ziegler reactions. The composite was developed hydrothermally from microcrystalline cellulose (MCC), iron chlorides, urea, and hydrochloric acid at 180 °C for 20 h in a one-pot reaction. After collecting the magnetic CNCs (MCNCs), post-sulfonation was performed using chlorosulfonic acid (ClSO₃H) in DMF at room temperature producing sulfonated MCNCs (SMCNCs). The results confirmed the presence of sulfonated Fe₃O₄ and CNCs with a hydrodynamic size of 391 nm (±25). The presence of cellulose was beneficial for preventing Fe₃O₄ oxidation or the formation of agglomerations without requiring the presence of capping agents, organic solvents, or an inert environment. The SMCNC catalyst was applied to activate the Knoevenagel condensation and the Thorpe-Ziegler reaction with determining the optimal reaction conditions. The presence of the SMCNC catalyst facilitated these transformations under green procedures, which enabled us to synthesize a new series of olefins and thienopyridines, and the yields of some isolated olefins and thienopyridines were up to 99% and 95%, respectively. Besides, the catalyst was stable for five cycles without a significant decrease in its reactivity, and the mechanistic routes of both reactions on the SMCNCs were postulated.