Synthesis And Research Of Calix[4]arene Derivatives

Calixarene is one kind of macrocyclic compounds derived from the condensation of phenol with aldehyde. With ease of sythesis, much more functionality, persistent shape and size as well as easily chemical modification calixarenes are named as the third generation superamolecular hosters and have been used as the platforms for so many types of chemical researches.Calixarenes and dendrimers are two types of the most important host molecules in supramolecular chemistry. The link between calixarene and dendrimer has long been regarded as one of the most ambitious targets in this field. Calixarene-based dendrimers have some promising advantages and novel properties due to their unique structures consisting of both calixarene and dendrimer. They can be potentially applied to many fascinating areas such as smart materials, molecular devices and nano materials.Form 1997 thiacalixarene in which methylene bridge replaced by sulfur bond has been recongnized and quickly become new important class of synthetic host molecules and have versatile applications in supramolecular chemistry such as complex extraction, molecular devices, molecular recongnition, self-assembly and nanomaterials. The presence of sulfur atoms in place of the usual CH2 bridges makes thiacalix[4]arenas very interesting molecules, with many features that are not present in the chemistry of classical calixarenes. It is now obvious that these compounds posses some very uncommon features, different conformational preferences, and special complexation properties, and thus have many potential applications.In this paper we studied the synthesis of calixarene-based dendrimers and used thiacalix[4]arene as the platform for the synthesis of arylthioether. We hoped it could have some novel properties in molecular recognition,multiple recognition and self-assembly. The synthesis result of this paper as follows:1.We used the Williamson reaction to change the lower rim of the calixarene, then used the Sonogashira reaction to synthesis the shape of"Y","X"arylacetylene core. At last we got the dendrimers molecular used sonogashira reaction in high yield. We had also studied the process of some important reactions in the synthesis.2. We used one step reaction to synthesis of thiacalixarene, then used it as the platform for the synthesis of arylthioether compound. For the synthesis of the title compound we had been used Friedel-crafts reaction,NBS bromide,Williamson and Sonogashira coupling reaction.The structure of some intermediates and all target compounds synthesized in this paper were characterized by ¹H NMR, ¹³C NMR, and MS.