Syntheses And Binding Properties Of Calix[4]arene Derivatives With Semicarbazone And Benzalazine Groups

Regarded as "the third supramolecular receptor" along with crown ethers and cyclodetrins,calixarenes are a class of well defined macrocyclic oligomers of phenols bridged by methylene groups.Owing to their unique three-dimensional cavities, convenient preparation in large quantities,versatile complexation and recognization abilities towards ions or molecules;they have received considerable attentions in recent years.Due to easy modification on both lower and upper rims,the parent calixarenes frequently serve as molecular scaffolds for the construction of more elaborate supramolecular systems.Calixarenes or biscalixarenes containing heteroatom groups have good complexation and recognization abilities for transition metal and heavy metal cations.Some of them also have good spectroscopy properties.They can be broadly used in the fields of chemical analysis,ions sensors,etc.In this thesis,the syntheses, characterization,complexation properties,and UV spetra properties of several novel aza-calix[4]arene and benzalazine bis-calix[4]arenes are described in details.Firstly,a new calix[4]arene derivative with Schiff-base and thiourea units was synthesized.Its extraction properties for metal cations and amino acids were investigated. It possessed good complexation selectivity for soft metal cations.Secondly,calix[4]arene mono-benzaldehyde and di-benzaldehyde derivatives were synthesized under definite reaction conditions.Then they reacted respectively with hydrazine hydrate by "2+1" or "2+2" condensation reaction to obtain two novel benzalazine-bridged bis-calix[4]arenes. Their absorption properties towards metal ions and UV-vis spectra were investigated. Their UV/vis spectra showed a red shift upon the addition of the transition or heavy metal ions.Besides,a dentritic calix[4]arene derivative containing benzalazine groups was also synthesized by reacting calix[4]arene di-benzaldehyde derivatives with salicylide hydrazone.At last,we synthesized a new calix[4]arene derivative bridged by semicarbazone on the lower rims.It was found that this compound exhibited good extraction towards metal ions and amino acids,and formed 1:1 complexation with arginine.