SYNTHESIS AND PHASE-TRANSFER CATALYTIC ACTIVITY OF CROWN ETHERS BOUND TO MICROPOROUS POLYSTYRENE RESINS BY OXYETHYLENE SPACERS

Crown ethers bound to microporous polystyrene resins by oxyethylene spacers were prepared by the reaction of monoazacrown ethers with 2-tosyloxyethoxymethylated or 2-(2-tosyloxyethoxy)ethoxymethylated polystyrene resins crosslinked with 2 mol % of divinylbenzene. The activity of the immobilized lariat crowns for halogen exchange reactions under triphase conditions has been studied as a function of catalyst structure, loading, substrate structure, reagent structure, and solvent. The lariat catalysts with extra oxygen donors in the spacer chain exhibited higher activity than the corresponding immobilized catalysts without the donors in the spacer. The increased activity of the catalyst containing 15-crown-5 unit and two extra donors for the reaction of 1-bromooctane with KI was concluded to result from the enhanced complexation with the K+ ion, induced by the cooperative coordination of the crown unit donors and the donors in the spacer chain. The recovered catalysts could be re-used without decrease in activity.