The Syntheses And Properties Of Novel P-tert-butylcalix "6" Arene Aza Derivatives

Calixarenes are the third generation of the host molecules, as a building block to construct the novel host molecules with good recognition abilities towards the guests. Recently, people have paid much attention to O, N, S-bridged calixarenes. Calixarene derivatives containing amide, thiourea and urea units have good recognition abilities towards the guests. Therefore, studies on their derivation and recognition properties are in the ascendant. The study of calix[4]arenes has approached maturity, much attention has been paid to the next member of calixarenes family, calix[6]arenes. In comparison with calix[4]arene composed of four phenolic units, calix[6]arene is constructed by six phenolic units, which results not only in more kinds of derivatives, but also in more conformation mobility than that of calix[4]arene. In order to recognize guest molecules precisely, a rigid, conformationally-defined calixarene is essential. To freeze the conformation of calix[6]arene, a route is bridging of two or capping of three or more phenolic rings. In this paper, a series of p-tert-butylcalix[6]arene derivatives are designed and synthesized. Their complexation properties and liquid membrane transport properties are also studied.Firstly, we designed and synthesized a series of hexa-substituted p-tert-butylcalix[6]arene derivatives, tetra-substituted p-tert-butylcalix[6]-1,4-crown-4 derivatives and triply bridged p-tert-butylcalix[6]arene derivatives, and the complexation properties of the synthesized compounds to Na+, K+, Cs+, Zn2+, Cd2+, Hg2+, Ni2+, and Ag+ were studied by extraction experiments. Secondly, the liquid membrane transport of K+, Zn2+ and Ag+ with the synthesized compounds as carrier has been investigated. The effects of the related factors on the transport were studied. Finally, a new p-tert-butylcalix[6]crown-based polymer was synthesized and characterized by IR spectroscopy and surface scanning electron microscope. The complexation experiments demonstrated that the polymer showed excellent extraction property towards Hg2+, and the extration capabilities of the polymer for Hg2+ was 3.45mmol/g.