Synthesis And Properties Of Azo-Calix[4]Arene Carboxylic Acid And Its Derivatives

It is well known that " Calixarene is the hosts molecules with almost unlimited possibility".It does not only own unique self-assembly ability, but also its strucrer is flexible,and its has many points modified。Because of calixarene has so many chacharacteristic that the study about chemical derivatization of calixarene become a hot topic gradually in the area of super molecular chemistry. The main work of this paper based on calix[4]arene containing ester group, introduced azo-group into the upper rim and carboxy group groups into the lower rim respectively, design and synthesis of a series of containing azo or imine calix[4]arene, mainly through the fluorescenceUV-vis spectrum inspecting them complextion with metal ions.This paper is mainly divided into four parts, the first chapter is the introduction of development of calixarenes. Calixarene is a ring oligomer with linkage of the methylene bridge or a similar group and a hole inside by condensation reaction of alkyl phenol and formaldehyde.Owing to flexible structure, easy modification, capacity to complex with many kinds of cations, anions as well as neutral molecules, changable cavity size etc,there are wide attentions have being attracted.Calixarene is mainly modified at the upper rim and at the lower rim. Diazo-coupling reaction is an important method used to modificate the upper rim of calixarene. Introducing -N=N- as coloration group, may make calixarene form the host molecule of color change. The modifications at the lower rim of calix[4]arene are mainly by the chemical activity of phenolic hydroxyl group. The chiral groups, optical active and electrical active groups, hydrophilic group and so on could be connected to calix[4]arene by the phenolic hydroxyl groups at the lower rim. The calix[4]arene derivatives have selectively recognition abilities to kinds of ions.The next two chapters are the main parts of the paper. Main content is as follows:① Two precursors of calixarene were synthesized,p-tert-butylcalix[4]arene and calix[4]arene and calixaren.② By selective etherisation, the calix[4]arene derivative with different unit (ethoxycarbonyl)methoxy at the lower rim were synthesized:25,-(ethoxycarbonyl)-methoxy-26,27,28-trihydroxycalix[4]arene(compound C); 25,27-bis[(ethoxycarbonyl)-methoxy]-26,28-dihydroxycalix[4]arene (compound D); 5,26,27-tri[(ethoxycarbonyl)-methoxy]-28-hydroxycalix[4]arene (compound E).③ A series of azocalix[4]arene derivatives contained different methylphenyl were synthesized based on above three intermediate compounds。All above azocalixaren were hydrolyzed to give a series of azocalixarens contained carboxyl group at the lower rim.All 10 carboxylic caid componuds have never been reported.④ All of the products are characterized by IR and’H-NMR.13C-NMR A part of the products are characterized by ESI-MS.⑤ The recognition of ten compounds were mensurate by UV-vis spectrum. From the result,we know that all the carboxylic acid compound T-oMBA has the recognition ability to rare earth metail ions,especially Y3+.⑥ The fourth chapter is the conclusion of the paper and discussion of further work.