Synthesis Of Calix[4]Arene Derivatives And Their Interaction Properties With Metal Ions

The pollution of metal ions, especially the heavy metal ions is becoming more and more urgently to be solved. The recognization and adsorption of Calixarenes to metal ions become an effective way to detect and dispose metal ions. The synthesis of N-carboxylic acid Calix[4]arene azacrown-5and azacrown-6, sulfonic Calix[4]arenehydrazide, the recognization, adsorption and interaction of these compounds to metal ions were researched in this paper.1. Four new compounds4a,4b,5a,5b were obtained by N-acylation reaction of succinic anhydride and maleic anhydride, with the cyclized molecules which were formed by ring-closed reaction of25,27-di(ethoxycarbonyl methoxyl)-26,28-dihydroxyl calix[4]arene (3), coming from a three-steps reaction using p-tert-butyl phenol as a starting material, with diethylenetriamine and triethylenetetramine, respectively. Their structures were characterized by1H NMR,13C NMR, MS, FT-IR. The adsorption properties of these four compounds to metal ions were studied preliminarily in solid-liquid adsorption. Results showed that they exhibited good adsorption selectivity to Pb2+and Cd2+, the adsorption behavior is better described by the Langmuir isotherm, it’s calculated that the saturation adsorption amount for Cd2+ion adsorption onto compounds4a,4b,5a,5b are0.222,0.159and0.210,0.161mmol-g’1, respectively;0.672,0.609and0.632,0.576mmol-g’1for Pb2+, respectively.2.25,27-di(hydrazide methoxyl)-26,28-dihydroxyl calix[4]arene (compound7) was synthesized by the reaction of compound3and hydrazine hydrate, two water soluble compounds:sulfonic calix[4]arene lower rim dicarboxyl acid (compound6) and sulfonic calix[4]arene lower rim dihydrazide (compound8) were obtained by sulfonation reaction of compound3and7with concentrated sulfuric acid, respectively. Their structures were characterized by1H NMR,13C NMR, MS and FT-IR. The UV spectral changes of these two compouds after addition of metal ions were researched. Result showed that, for compound6, when Ca2+was added, the maximum absorption wavelength blueshifted, and absorbance increased; and for compound8, at pH5.5-6.5, after the addition of Cd2+, Ca2+and Mn2+, the maximum absorption wavelength blueshifted significantly, and absorbance increased. At pH5.5, Cd2+over4mg-L"1can be recognized when the concentration of compound8is100mg·L-1.