Design And Synthesis Of Novel Oxa-/Aza-Calixarene Derivatives

There is no doubt that the advent of heterocalixarenes has brought new horizons for supramolecular chemistry. Heterocalixarenes have been not only providing unique models in the study of noncovalent molecular interactions, but also serving as building blocks in the construction of high-level molecular and supramolecular architectures and in the fabrication of molecular devices and advanced materials. The design and synthesis of novel and functional heterocalixarenes has become a certain direction of supramolecular chemistry with the demand of diversity. Based on these proofs, firstly, we expound the present research about heterocalixarenes. Secondly, we report the design and synthesis of a series of oxacalixarenes derivatives. Next, we report the design and synthesis of a series of azacalixarenes derivatives. Finally, we report the design and synthesis of a series of unsymmetrical N and/or O-bridged calixarene derivatives.In chapter1, the first azacalixarene and oxacalixarene may date back to the1960s. But until recently, we witness the systematic development of heterocalixarenes. Herein, a detailed review was carried out about their research progress with a classification according to different atoms, such as N, O. We put forward our design ideas and research topics based on the above review.In chapter2, we synthesized a series of oxacalixarenes derivatives under very mild reaction conditions with phenols and cyanuric chloride as nucleophilic reagent and electrophilic reagent respectively via one-pot method. We also analyzed the crystal structure of some targeted compounds in detail.In chapter3, we synthesized a series of azacalixarenes derivatives under very mild reaction conditions with arylamines and cyanuric chloride as nucleophilic reagent and electrophilic reagent respectively via one-pot method. We also analyzed the crystal structure of some targeted compounds in detail.In chapter4, we synthesized a series of unsymmetrical N and/or O-bridged calixarene derivatives by means of mixing different phenols and arylamines with cyanuric chloride under mild conditions via fragment coupling. We also analyzed the crystal structure of some targeted compounds in detail.