Syntheses And Properties Of Thiacalixarene Aza-crown Ether And Its Relative Derivatives

Calixarenes are utilized as building blocks to construct the novel host moleculeswith good recognition abilities towards the guests, which have attracted considerableattention for researchers. Recently, people have paid much attention to calixarenesbridged by heteroatom, especially the study of thiacalixarene, which becomes a newhot molecule in calixarenes chemistry. Because its four S atoms substitute for bridging-CH₂, thiacalix[4]arenes exhibit different properties from "classical" calixarenes,therefore, studies on their derivation and recognition properties are in the ascendant.In this paper, thiacalixarene is used as a building block, and a series ofthiacalix[4]arene derivatives and polymers are designed and synthesized, and theirbinding properties towards metal cations and amino acids are studied.In this thesis, we first synthesize a series of thiacalixarene aza-crown ether and itsrelative derivatives with the structure of bridging or open-chain, such as ester, amide,schiff base and thiourea derivatives. Metal cation extraction experiments demonstratethat thiacalix[4]arene derivatives containing amide and thiourea units shows betterextraction property towards soft metal ions Ag⁺ and Hg²⁺. And amino acid extractionexperiments suggest that this derivative exhibits excellent extractability towardsamino acids. UV-vis and ¹H NMR are used to study the binding property ofthiacalixarene aza crown ether towards a series ofα—amino acids, and their bindingconstants are calculated. The results show that it possesses good complexationabilities towardsα—amino acids, and complex compound of 1:1 is formed betweenhost and guest molecules.First example of thiacalixarene polymer that contains schiff base unit and possessesthe stereo and netted structure has been synthesized. This polymer possesses novelstructure and N- and S- functional group, and exhibit outstanding adsorption propertytowards cations, expecially for Cd²⁺ and Hg²⁺.