Synthesis Of Heterocyclic Ring Derivatives Of Calix[4]arene And Properties For Their Cations Extraction

The rational design and preparation of calixarene derivatives with tailored structures and special functions as host compounds is one of the main focuses in supromolecular chemistry. In this thesis, derivatives of heterocyclic thioalkoxycalix[4]arene on the lower rim and heterocyclic thioacetamidecalix[4]arene on the upper rim have been designed and prepared. A total of thirty new compounds have been synthesized and characterized. Their extraction properties have been studied by metal picrates liquid-liquid extraction and the results show:By using three thio-heterocyclic compounds, twelve novel derivatives of thioalkoxycalix[4]arenes on the lower rim have been synthesized and structurally characterized by 1H NMR,13C NMR,IR and MS. Among them, nine compounds adopt cone conformation and other three compounds adopt the mixture conformation due to the influence of the methyl groups on the lower rim. A single-crystal structure of a new compound [7a: 25,27-bis(4,5-dihydrothiazolyl-2-thiopropoxy)-26,28- dihydroxy-5,11,17,23-tetra-t-butylcalix[4]arene] has been determined by X-ray diffraction measurement. The structural analysis shows that a cavity of 6.697(3)A x 7.408(3)A is formed.With introducing five thio-heterocyclic compounds into calix[4]arene on the upper rim after ipso-nitration, reduction, bromo-acetamidation and substitution on heterocyclic ring reactions, we have successfully obtained eighteen new compounds including three new intermediates. All these compouds are confirmed by 1H NMR,13C NMR,IR and MS and the data means that all of them adopt the cone conformation. A single-crystal structure of a new compound [15b: 5,17-di(5-methyl-1,3,4-thiadiazolyl-2-thiaacetamidyl)-11,23-tetra-t-butyl-25,27-dihyd-roxy-26,28-diethoxycalix[4]arene] has been determined by X-ray diffraction measurement. The structural analysis shows that a cavity of 6.86(3)? x 6.36(3)? is formed.Liquid-liquid extraction experiments, between twelve heterocyclic thioalkoxycalix[4]arene on the lower rim, fifteen heterocyclic thioacetamidecalix[4]arene on the upper rim and Na⁺,K⁺,Cs⁺,Mg²⁺,Cu²⁺,Co²⁺,Cd²⁺,Ni²⁺,Pb²⁺,Hg²⁺ and Ag⁺ picrates, have been carried out and their results are compared. This study shows that all of these compounds exhibit good extraction abilities toward Ag⁺ and Hg²⁺, and the highest extraction percentages are 38.4% and 40.5%, respectively, toward sliver and hydrargyrum picrates. Interactions between the two series of calixarene and transitional metals are deduced and the influence of the subsituents on the extraction percentage is analysized.