The Synthesis,Extraction Properties Of P-tert--Butylcalix[n]aryl Ester,Amide And Azo Derivatives

Recent advances in host-guest chemistry demand more and more sophisticated artificial host moleculesles. In order to realize such molecules, the functional modifications of calixarenes is of primary importance, and continue to attract much attention not only due to their interesting molecular structure, but also due to their formation of versatile derivatives. p-tert-butylcalix[4]arenes have mostly used as a platform for the preorganization of building site due to its small size. While the larger calix[n]arenes (n = 6, 8) appear more suitable to play the role of a molecular receptor and are attracted much attention in recent year. Our goal is to extend and to develop some new functionalized calix[n]arenes (n = 6, 8) supermolecular system. In this thesis we initiated the studies on syntheses and extracting powers of tert-butylcalix[n]arene derivative and achieve a series of interesting experiment results.1. Twenty-six new calix[n]arenes derivatives (n = 6, 8) were synthesized and fully characterized by NMR, IR and UV spectroscopes, which include long chain ester ether, amide, azo and thiourea compounds.2. By thorough alkylation reaction, four new ester substituted calixarene derivatives containing long ethylene glycol ether chain units were prepared. Their complexing abilities to alkali and transition metal cations were studied with the UV spectroscopy.3. The N, N-dialkyl substituted calix[n]aryl amide derivatives were synthesized in high yields by the direct alkylation with chloroacetamides or by amination of previously prepared calixaryl esters. These amides show high selective extraction for transition metal ions.4. From the amination reactions with ethylenediamine and dimethyl propylenediamine, the amide derivatives containing active amino groups were prepared, which in turn transferred to' thiourea derivatives with reaction of phenyl isothiocyanate. Their extraction experiments showed that the selective ability were affected by the cavities of calixarenes and the radius of metal ions.5. Five chromogenic azo calixarene derivatives were prepared by alkylation of calixarenes with chloroacetyl 4'-amino-2, 3'-dimethylazobenzene. Their complexing and extracting properties for alkali, alkali earth and transition metal cations were studied with UV-Vis and atomic absorption methods...