Quaternary ammonium functionalized polyacrylonitrile fiber supported phosphotungstic acid as efficient heterogeneous catalyst: Hydrophobic tuning of the catalytic microenvironment

Abstract

Thirteen novel amine or quaternary ammonium functionalized polyacrylonitrile fiber (PANF) supported phosphotungstic acid (PTA) catalysts were designed and prepared, and their catalytic activities were screened by choosing condensation/annulation tandem synthesis of 2,3-dihydroquinazolin-4(1H)-one compound via C–N bond formation between 2-aminobenzamide and p-chlorobenzaldehyde as a model reaction. By adjusting the functionality and hydrophobic/hydrophilic property of the amine/ammonium structure as well as the density of PTA sites, the fiber catalyst CAT-12 prepared from quaternary ammonium functionalized PANF containing benzyl group with high PTA loading achieved the best catalytic activity for most reactions in water. The CAT-12 can be easily separated from the reaction system and recycled for 7 times without significant loss of catalytic activity. Moreover, the reaction proceeded smoothly in gram scale and gave nearly quantitative yield using this efficient, eco-friendly and easily recyclable catalyst with great industrial potential which was also demonstrated in Friedel-Crafts alkylation of indoles with β-nitrostyrene. Vivid PTA immobilization processes and the corresponding “catch-catalyze” catalytic modes were further schematically described to address the effect of microenvironment-tuning on immobilization and catalysis, and accordingly the possible catalytic mechanisms of the two reactions were proposed.