Zeolite-based organic-inorganic hybrid catalysts for phosgene-free and solvent-free synthesis of cyclic carbonates and carbamates at mild conditions utilizing CO_2

摘要

As-synthesized zeolite-beta exhibits high catalytic activity for the synthesis of cyclic carbonates and alkyl and aryl carbamates by a phosgene-free route,utilizing the greenhouse effect gas CO_2.The reaction occurs with high yields of the desired products at mild conditions and without using any solvent or cocatalyst.Cyclic carbonates are synthesized by cycloaddition reaction of CO_2 with oxiranes (epichlorohydrin,propene oxide,styrene oxide and n-butene oxide) at 393 K and 6.9 bar.Alkyl and aryl carbamates are synthesized by the reaction of the corresponding amines,CO_2 and n-butyl bromide at 353 K and 3.4 bar.The as-synthesized zeolite-beta containing the encapsulated quaternary ammonium ions is not only reusable in several recycling experiments,but also shows superior activity to that of the corresponding homogeneous,quaternary ammonium halide salt generally used in the commercial synthetic practice.The microporous silica (inorganic) acting in concert with the encapsulated organic component constitutes an efficient,recyclable catalyst for this reaction.