Novel lariat calix[4]-1,3-aza-crowns with two branched chains — The excellent phase transfer catalysts for nucleophilic substitution reaction

Abstract

By reacting calix[4]-1,3-diethoxylaminoethyl derivative (2) with phenyl isothiocyanate, novel dendritic calix[4]arene derivative (3) with two different branched chains was synthesized in a yield of 78%. By reacting compound 2 with 1,6-diisocyanatohexane or N,N′-bis(2-chloracetamide)ethylene in a “1 + 1” intermolecular addition mode, novel lariat calix[4]-1,3-aza-crowns (4 and 5, respectively) with two branched ethoxyl chains were prepared in reasonable yields. The composition, structures, and conformations of all new compounds were confirmed by elemental analyses, IR, ESI-MS, 1H NMR, and so forth. The liquid–liquid extraction experiments showed that all new hosts possessed good extraction abilities towards soft and hard metal cations. The liquid membrane transport experiments suggested that they had good transport abilities for K+ and Ag+. The experiments of phase transfer catalysis indicated that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimum yields of products in catalytic reaction were as high as approximately 100%.