Synthesis And Properties Of Aniline-modified Semi-cucurbitacin Derivative

Supramolecular chemistry is one of the research hotspots in the field of chemistry.Supramolecular chemistry is the study of the aggregation of molecules formed by combination of two or more molecules through intermolecular forces.Macrocyclic compound,as one of the most important parts in supramolecular chemistry,has attracted researchers to construct.Hemicucurbit[n]urils as a new macrocyclic compound,has attracted much attention from researchers since it was reported by Miyahara in 2004.Due to the lack of binding sites between Hemicucurbit[n]urils and guest molecules,it is difficult to derive,etc.,which limits the extensive application of Hemicucurbit[n]urils.Therefore,the synthesis of new modified hemicucurbituril is of great significance for the research vitality of hemicucurbit[n]urils macrocyclic compounds.As a new type of modified hemicucurbituril synthesized by our research group,aniline modified hemicucurbituril has the property of derivatization.Therefore,the structure of aniline modified hemicucurbituril is used as the basic framework for a series of studies in this paper.The thesis mainly consists of the following two parts:（1）Modification of hemicucurbituril by acylated anilineAmide groups are widely used in supramolecular chemistry as anion receivers.In this paper,the reaction conditions of synthesis of amideated aniline modified hemicucurbituril derivatives were investigated,and a new type of aniline-modified hemicucurbituril macrocyclic compound containing ethyleneurea and sulfonamide group was prepared.The supramolecular chemical properties of the macrocyclic compound and small organic molecules were explored.Its structure was characterized by ¹H NMR,¹³C NMR and mass spectrometry.By NMR titration experiment combined with Job method,the binding ratio and binding constant between the sulfonamide macrocyclic compound and the object were investigated.（2）Study on modified hemicucurbituril containing azo structurePhotocontrolled supramolecular reversible systems based on macrocyclic and azo compounds have been a hot topic in recent years.The excellent optical properties of the complexes of the two have attracted great attention in the fields of catalysis,molecular machine design and smart materials.In this paper,the synthesis conditions of the symmetrical azo macrocyclic compound were investigated by using the structure of aniline-modified hemicucurbituril derivatives as the framework.A new symmetrical azo macrocyclic compound containing ethyleneurea was synthesized by the reduction of nitro compounds.The photoisomerization behavior of the symmetrical azo macrocyclic compound was also studied.The structure of the bicyclic macrocyclic compound containing azo structure was characterized by ¹H NMR,¹³C NMR,mass spectrometry and X-ray diffraction.Based on the presence of trans-isomerism and cis-isomerism in azo compounds,the photostable equilibrium between the planar trans-isomer and the twisted cis-isomer plane was established under ultraviolet and visible light irradiation.The photoisomerization behavior of the azo compounds was studied by UV-visible spectrophotometer.The results showed that these compounds could achieve rapid photostability under ultraviolet irradiation.It has good reversibility and stability.