Synthesis and Complexation Abilities of Novel Multiple-Sites Calix[4]arene Receptors: Calix[4]arene Derivatives with Anthraquinone Groups on Lower Rims and Hydrazone Groups on Upper Rims

By formylation of 1,3-bisubstituted calix[4]arene anthraquinone derivative 1 in hexamethylenetetramine/trifluoroacetic acid system, the corresponding formylated gecalix[4]arene anthraquinone derivative 2 was synthesized in yield of 63%. By further reacting compound 2 with salicylic hydrazide, 2,4-dinitrophenyl hydrazine, nicotinyl hydrazine or phenyl thiosemicarhazide, novel calix[4]arene derivatives with anthraquinone and hydrazone groups 3a-3d were obtained in yields of 74-83%. The extracting experiments for series of metallic cations showed that compounds 3a-3d possessed high extracting abilities and extracting selectivity for tested cations. The complexation UV-Vis spectra for a series of anions indicated compounds 3a-3d exhibited the strong complexation abilities for tested anions. The H-1-NMR titration study showed that compound 3d possessed excellent complexation abilities for ion-pair of NaH2PO4 in 1:1 host-guest complex with the association constant of 4.6 x 10(4) M-1.