Study On Synthesis Of Calixarene Imidazolium Salts And Functionalized Cyclotriveratrylenes

During the past decades, people have paid considerable attention to calixarenes, which are known as the third generation supramolecular compound after cyclodexitrins and crown ethers. Now many functional calixarene derivatives have been synthesized and reported. By the introduction of various functional groups, calixarenes can change its cavity, enhance the ability of coordination and the ability to identify some molecules and ions. Recently another supramolecular compound, cyclotriveratrylene, has become the new attractive host molecule. Cyclotriveratrylenes and calixarene have similar physical and chemical properties. In this thesis, these two kinds of supramolecular compounds were chosen as the research topics. We have synthesized a series of functionalized calixarene and cyclotriveratrylene derivatives and studied their crystal structures, complexing properties and application in nano materials. Some interesting research results are as follows:1.p-t-Butylcalix[4]arene and p-t-butylthiacalix[4]arene were alkylated with versatile dibromoalkane with potassium carbonate as base to give respectively1,3-dibromoalkylcalix[4]arenes and tetrabromoalkylthiacalix[4]arenes. Then these bromoalkylcalixarenes reacted with N-methylimidazole, N-butylimidazole and N-benzylbenzimidazole in refluxing toluene to give the corresponding calixarene imidazolium salts. The transition metal such as Cu, Ag, Hg complexes of N-heterocyclic carbens were successfully prepared by coordination reactions and determined by X-ray diffraction.2. A series of tetramethoxyl resorcinarenes bearing with four alkyleneimidazolium salts were succefully obtained by similarly two-setp reactions. Tetramethoxyl resorcinarenes were firstly alkylated with dihaloalkanes in basic system to result the tetrasubstituted haloalkyl resorcinarenes, which in turn reacted with N-methylimidazole, N-butylimidazole to finish the formation of imidazolium salts. The strutures of all prepared compounds were fully characterized with spectroscopic methods and some were confirmed by X-ray single crystal diffraction.3. Cyclotriveratrylene triacetates were efficiently prepared by Lewis acid condensation of O-methoxyphenyl acetate with parafomaldehyde. From which several cyclotriveratrylene functionalized acylhydrazine, amide, acylurea, and Schiff bases were obtained. The water soluble cyclotriveratrylene amides were successfully applied in the stabilization of Au nanoparticles and the self-assemble properties of them in water were also investigated.