Synthesis Of P-tert-Butylcalix[4]arene Derivatives And Studies In Their Properties

Calixarenes, the third generation supramolecular compound,are more liable to chemical modification,from which thousands of calixarene derivatives with versatile properties can be derived. Thus its have been attracted great interests in home and abroad. Calixarenes and their derivatives can form complexes with lots of metal ions,inorganic anions and organic little molecules.Taking advantage of its easily modified characteristic,its applications in molecule recognition, extract separation and electrochemical sensor are receiving increasing attention.In this paper, two classes of calixarene derivatives were synthesized and their extraction properties toward inorganic anions were studied. Ag-AgCl solid reference electrode was prepared in this paper.Ag-AgCl solid receference electrode was prepared with Urea-formaldehyde resin and polyethylene glycol as frame materials. The optimal proportion among urea-formal- dehyde resin, polyethylene glycol and potassium chloride was investigated. The results show that when the weight percentages of urea-formaldehyde resin, polyethylene glycol and potassium chloride are 60%,20% and 20% respectively, the electrode can obtain optimal and reliable properties.The conditions for synthesis process of 5,11,17,23-tetra-tert-butyl-25,26,27,28- tetrahydroxycalix[4]arene and 5,11,17,23-tetra-tert-butyl -25,27-bi(ethoxycarbonylmet- hoxy)-26,28-dihydroxycalix[4]arene was optimized through orthogonal experimence. Reacting aldehyde with calix[4]arene hydrazine derivative which was obtained by treatment of 5,11,17,23-tetra-tert-butyl-25,27-bi(ethoxycarbonylmethoxy)-26,28-dihyd- roxycalix[4]arene with hydrazine hydrate.A series of calixarene schiff derivatives containing pyridinyl,dimethylaniline,thiophene group,furan group and benzene group respectively were synthesized in high yield.Calixarene carboxylic derivatives was obtained through hydrolyze 5,11,17,23-tetra-tert-butyl-25,27-bi(ethoxycarbonylmethox- y)-26,28-dihydroxycalix[4]arene in alkaline circumstances,from which 5,11,17,23-tetra -tert-butyl-25,27-bi(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene was further derived.These compound were all characterized by 1H NMR and IR.The calixarene derivatives extraction properties were studied for inorganic anions,such as Cr₂O₇^2-,SO₄^2-,NO₃^-,NO₂^-,Cl^-,PO₄^3-,C₂O₄^2- by liquid-liquid extraction. The results indicated calixarene derivatives containing pyridinyl or dimethylaniline have high extraction selectivity for Cr(â…¥) in acidic circumstances. The reverse extraction properties of NaOH to Cr(â…¥) in organic phase and reverse extraction yied following shaken time were studied.