Synthesis Of Difuncational Schiff Bases And Terpyridines On Calixarenes And Thiacalixarenes

As the third generation supramolecular host compounds, calixarenes, along with the cyclodextrins and crown ethers, are new types of macrocyclic compounds. Calixarenes are attracted much attention due to their unique cavity building, high melt pointing, high stability, adjustable phenolic units and many excellent supramolecular chemical and physical properties. Through the modification of the upper-rim or lower-rim calixarenes can be transformed to versatile functionalized derivaes, which have been successfully used in molecular recongination, mimic enzyme catalysis, chemical sensor, self-assembly and nano research fields. In this work we used calixarene as platform to introduce some coordinated functional groups and synthesized a series of calixarene difunctional derivatives.1. Through the O-alkylation ofω-chloroalkoxybenbenzaldehyde, calixarene dialdehyde derivatives have been synthesized, which in turn reacted with semicarbazide and thiosemicarbizide to form a series of calixarene-based semicarbazone, thiosemicarbazone. Some calixarene sulfur-containning Schiff base derivatives are also prepared by the condensation with S-methyldithiocarbazate or S-benzyldithiocarbazate. Their structures are characterized by IR, 1H NMR and 13C NMR spectroscopy and were further confirmed by X-ray diffraction determination of representative single crystals.2. The key building block 2,6-bis(2-pyridyl)-4-pyridone was prepard efficiently and were further mono-alkylated with alkylene dihalide to give chloroalkoxyl terpyridines. Then by direct O-alkylation reaction two or four functionalized terpyridine units were successfully introduced on the lower-rim of calixarene and thiacalixarene. Their structures are characterized by IR, 1H NMR and 13C NMR and spectroscopy and were further confirmed by X-ray diffraction determination of two single crystals.3. A series of alkoxy-bridged dibenzaldehydes have been synthesized, which in turn reacted with indole and 4-hydroxycoumarins to give alkoxy-bridged tetraindolyl and tetracoumarin derivatives in very convenientmanner. The structures of the synthetic bis(indolyl)methanes and coumarines were characterized with 1H NMR, 13C NMR, IR, MS and were further confirmed by X-ray diffraction determination of two single crystals.