Preparation of a Dual-Functionalized Acid-Base Macroporous Polymer via High Internal Phase Emulsion Templating as a Reusable Catalyst for One-Pot Deacetalization-Henry Reaction.

Abstract

A macroporous dual-functional acid–base covalent organic polymer catalyst poly(St-VBC)-NH2-SO3H was prepared using high internal phase emulsion polymerization using vinylbenzyl chloride (VBC), styrene (St), and divinylbenzene (DVB) as substrates toluene as a porogenic solvent, and subsequent modification with ethylenediamine and 1,3-propane sultone. The role of various amounts of toluene as the porogenic solvent as well as the amount of 1,3-propane sultone (different ratio of acid/base sites) on the structure of the prepared materials have been carefully investigated. The prepared materials were characterized by Fourier transform infrared (FT-IR), CHNS elemental analysis, energy-dispersive X-ray (EDX), elemental mapping, field emission scanning electron microscopy (FE-SEM), and thermalgravimetric analysis (TGA). The catalytic activity of the poly(St-VBC)-NH2-SO3H series with different acid/base densities was assessed for one-pot cascade C–C bond-forming reactions involving deacetylation–Henry reactions. The poly(St-VBC)-NH2-SO3H(20) sample bearing 1.82 mmol/g of N (base site) and 1.16 mmol/g (acid site) showed the best catalytic activity. The catalyst demonstrated superior activity compared to the homogeneous catalysts, poly(St-DVB)-SO3H+EDA, poly(St-VBC)-NH2+chlorosulfonic acid, and poly(St-DVB)-SO3H+poly(St-VBC)-NH2 as the catalyst system. The optimized catalyst showed excellent catalytic performance with 100% substrate conversion and 100% yield of the final product in the one-pot production of β-nitrostyrene from benzaldehyde dimethyl acetal under cascade reactions comprising acid-catalyzed deacetalization and base-catalyzed Henry reactions. It was shown that these catalysts were reusable for up to four consecutive runs with a very slight loss of activity. The excellent performance of the catalyst was attributed to the excellent chemical and physical properties of the developed support since it provides an elegant route for preparing site-isolated acid–base dual heterogenized functional groups and preventing their deactivation via chemical neutralization.