Study On Synthesis And Properties Of Functional Calix[4]resorcinarene Derivatives

Calix[4]resorcinarenes represent an important class of synthetic host molecules and have versatile applications in supramolecule chemistry such as complex extraction, molecular devices, molecular recognition, self-assembly and nano materials. We initiated the studies concerning the synthesis and properties of some functional calix[4]resorcinarene derivatives, and have maken a series of significant and creative results. The main results are showed as follows:1. Tetramethyl, tetraphenyl, tetra-p-hydroxyphenyl and tetraferrocenyl calix[4]resorcinarenes are alkylated with different alkylation reagents to give a series of functional derivatives such as esters, chloropropyl, cyanopropyl, amides. Then the calix[4]resorcinarenes esters derivatives reacted with diamines or hydrazine to give amide with terminal amino groups, or hydrazone derivatives, which in turn condensated with pyridinecarboxaldehyde and ferrocenecarboxaldehyde, acetoacetone to yields Schiff bases and ketoimine derivatives. Their structures are characterized by NMR and IR and elemental analysis and confirmed by determination of eleven single crystals.2. Efficient prodedure was developed for selectively and efficiently introducing ferrocenyl groups on the upper rim, or on the lower rim, or both on the upper and lower rims of resorcinarenes. The electrochemical properties of these ferrocene-containig resorcinarenes were studied by Cyclic Voltammetry(CV) and Differential Pulse Voltammetry(DPV).3. Two efficient procedures were developed for synthesing resorcinarene amide derivatives. One procedure is direct alkylation of resorcinarens with N,N-dialkylα-chloroacetamide in the system of K2CO3/ KI/acetone. The other is aminolysis of ethyl resorcinaryl acetates with aliphatic mono- and diamines in ethanol.4. Tetraphenyl, and tetraferrocenyl pyrogallol[4]arenes are prepared efficiently and their structures are confirmed by determination single crystals of acyl derivatives. From which It is interesting to find that tetraphenyl, and tetraferrocenyl pyrogallol[4]arenes exist in two different kinds of configuration.