Study On Synthesis And Properties Of Functional Tetramethoxyresorcinarenes And Cyclotriveratrylenes

Calixarenes are known as the third generation supramolecular hosters after crown ethers and cyclodexitrins. This class of molecules has been found versatile applications in number of research fields including molecular recognition, metal complexes, self-assembly, nano materials, catalyst and fluorescent probes as well as others. Recently the research and development of new kind of calixarene-type macrocycles are attracted much attention and has become one of most hot topics in supramolecular chemistry. Tetramethoxyresorcinarene and cyclotriveratrylene are two new members of calixarene family. In this thesis these two new kinds of calixarenes were chosen as the research platforms. We investigated systematically the efficient methods for chemical synthesis, funcational modification of them and prpepared a series of calixarene ester, amide, acylhydrazone and Schiff base derivatives. The complexing properties of the prepared functional molecules for transition metal ions were also studied with UV-vis and fluorescent spectroscopy. The main achieved research results are as follows:1. Tetramethoxyresorcinarene with aliphatic and aromatic groups were conveniently prepared by the condensation of 3-methoxyphenol with various aldehydes under the Lewis acid catalysis. Tetramethoxyresorcinarenes can be efficiently alkylated with chloroacetate to give activated ester derivatives, which in turn were ammonolyzed with hydrazine or diamines to give hydrazone and amide derivatives. The tetramethoxyresorcinarene Schiff bases could be prepared by the condensated of above hydrazones with salicyladehyde. The activated esters can also be hydrolyzed or reacted with aminomethylpyridine to give acid and pyridylamidederivatives. The structures of all prepared new products were characterized by 1H NMR and IR spectroscopy, and further confirmed by X-ray diffraction determination of eight single crystals.2. Catalyzed condensation reactions of aldehyde with benzoyl, and tosyl 2-methoxyphenol or methyl (2-methoxy)phenoxyacetate were investigated and some important intermediates for chemical modification of cyclotriveratrylene were efficiently prepared. The cyclotriveratrylene triesters can be converted to a series of amide, acylhydrazone and Schiff base derivatives by the conventional methods. Their structures are characterized by 1H NMR and IR spectroscopy.3. The compexing proepties of the some representative tetramethoxyresorcinarene and cyclotriveratrylene Schiff bases for transition metal ions were studied with UV-vis and fluorescent spectroscopy. The compelxing constants and selectivity depending on the molecular structures were obtained.