The Syntheses And Properties Of Calix [4] Arene Aza-and Sulfur-derivatives With Branched Chain

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 convenient preparation in large quantities, unique three-dimensional cavities, chemical stability, high conformational variable, versatile complexation and re-cognization abilities towards ions or molecules; they have received considerable attentions in recent years. Due to easy modification on both lower and upper rims, appropriate functionalized calixarene derivatives have been widely used in molecular recognition, analytical chemistry, chemical sensing, analog enzymes, bio-medicine and other fields. Calixarene derivatives containing amide, thiourea and urea units have good recognition abilities towards heavy metal ions, transition metal ions and anions. Therefore, studies on their derivation and recognition properties and catalytic performance are in the ascendant. In this paper, calix[4]arene is used as a building block, and a series of calix[4]arene derivatives containing nitrogen and sulfur are designed and synthesized, and their binding properties and catalyst performance are studied.Firstly, we synthesized calix[4]arene derivatives with chiral amino alcohol fragment and branched chain. Metal cation extraction experiments demonstrate that new calix[4]arene derivatives show good extraction property towards both soft metal ions and hard metal ions. Because of the difference of structure, the two compounds show different liquid membrane transport properties. Compound 2 can be used as catalyst for esterification.Secondly, novel calix[4]arene bridged derivatives with acidamide and urea were synthesized by "1+1" condensation reaction. Their recognition properties and liquid membrane transport properties towards metal ions were investigated.Finally, compound 1 reacted respectively with ethyl thiol and mercaptobenzimida-zole in "1+2" condensation mode to obtain two novel calix[4]arene derivatives containing nitrogen and sulfur heteroatom. It was found that these two compounds exhibited good extraction and transport preporties towards metal ions.