Synthesis And Properties Of Carbonyl Calix[4]Arene And Its Derivatives

Calixarene is the third generation supramolecular host compound with unique cavity, which is the ideal molecular skeleton to build new structures and special properties. Introducing carbonyl into the framework of calixarenes, not only forming a reaction center which can complex with transition metal, but also can be used further modification of calixarene as a good intermediate. The main work of this paper based on calix[4]arene containing carbonyl, introduced azo-group into the upper rim and imine groups into the lower rim respectively, design and synthesis of a series of containing azo or imine calix[4]arene, mainly through the fluorescence spectrum inspecting them complextion with metal ions.This paper is divided into four parts, the first chapter is the introduction of calixarene development. 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. Because of flexible structure, easy modification, ability to complex with cations, anions and neutral molecules, changable cavity size and so on. it has attracted wide attention.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:①Two precursors of calixarene were synthesized,p-tert-butylcalix[4]arene and calix[4]arene.②By selective etherisation, the calix[4]arene derivative with bromine atom at the lower rim was synthesized.25.27-bis(2-bromoethoxy)-26.28-dihydroxycalix[4]arene (Compound C). Three calix[4]arene derivatives with carbonyl at the lower rim were synthesized.25,27-bis[2-(4-formoxylphenoxyl)ethoxy]-26,28-dihydroxycalix[4]arene (Compound D).25,27-bis[2-(2-formoxylphenoxyl)ethoxy]-26.28-dihydroxycalix [4]arene(Compound E).25,27-bis[2-(2-formylphenoxyl)ethoxy]-26,28-dihydroxy calix[4]arene(Compound F). The orthogonal experiment was used to optimize the synthesis of Compound E and improve the yield from23.6%to45.7%.③Compound E reacted with phenylamine,4-toluidine to form5,17-diphenylazo-25,27-bis[2-(2-formoxylphenoxyl)ethoxy]-26,28-dihydroxycalix[4]arene(Compound G) and5-(4-methylphenyl)azo-25,27-bis[2-(2-formoxylphenoxyl)ethoxy]-26,28-dihydroxycalix[4]arene(Compound H).Compound D reacted with phenylamine to form5,17-diphenylazo-25,27-bis[2-(4-formoxylphenoxyl) ethoxy]-26,28-dihydroxy calix[4]arene(Compound I).④Three kinds of Schiff base calix[4]arene derivatives were synthesized by Compound E with phenylamine,4-aminoantipyrine and a-naphthylamine.25.27-bis {2-[2-(N-phenylmethyleneamino)phenoxyl]ethoxy}-26,28-dihydroxycalix[4]arene (Compound J),25,27-bis{2-{2-[N-(4-antipyrine)methyleneamino]phenoxy1}ethoxy}-26,28-dihydroxycalix[4]arene(Compound K) and25,27-bis{2-{2-[N-(a-naphthyl) methyleneaminojphenoxyljethoxy}-26.28-dihydroxycalix[4]arene(Compound L).⑤All of the products are characterized by IR and’H-NMR. A part of the products are characterized by ESI-MS.⑥The recognition of Compound G and Compound K upon metal ions were investigated mainly by fluorescence spectra. The results show that Compound G has remarkable fluorescence enhancement (λem=408nm) when only added Co2+among the ions detected.Thus it has a special selectivity for Co2+. Compound K also has large fluorescence enhancement when added In3+(λem=399nm). Fluorescence enhancement is rarely reported comparing with fluorescence quenching.The fourth chapter is the conclusion of the paper and discussion of further work.