Synthesis And Properties Of Novel Azocalix[4]Arene Schiff Base Derivatives

Calixarene has widely application prospect in ions, molecular recognition and other fields. The main work of this paper based on calix[4]arene containing carbonyl, introduced azo-group and imine grounp into the lower rim, design and synthesis series of containing azo and imine calix[4]arene, mainly through the UV-vis spectrum inspecting them complextion with metal ions.This paper is divided into four parts, the first chapter is the introduction of calixarene development situation. The development of connectting azo-group or imide group into each rim of calixarene is closed to the mature. However, the research of connecting both of the groups into the lower rim is limited and the ions recognition research needs to be perfect.The next two chapters are the main parter of the paper. Main content is as follows:① A precursors of calixarene was synthesized Compound A.② By selective etherisation, the calix[4]arene derivative bromine atom at the lower rim was synthesized 25,27-dihydroxy-26,28-bis(2-bromoethoxy)-p-tert-butyl calix[4]arene (Compound B). Two calix[4]arene derivatives with carbonyl at the lower rim were synthesized 25,27-dihydroxy-26,28-bis{2-[(2-formoxyl)phenoxyl] ethoxy}-p-tert-butylcalix[4]arene(CompoundC) and 25,27-dihydroxy-26,28-bis{2-[(4-formoxyl)phenoxyl]ethoxy}-p-tert-butylcalix[4]rene (Compound D). The orthogonal experiment was used to optimize the synthesis D and improve the yield from 31.3% to 48.5%.③ Compound C reacted with 4-aminoazobenzene,3,2’-dimethyl-4-amino azobenzene,4-azobenzene-1-naphthylamine,4-(2-methylazobenzene)-1-naphthyl amine and 4-(4-methylazobenzene)-1-naphthylamine respectively to form 25,27-dihydroxy-26,28-bis{2-[2-(N-(4-azobenzene)phenylmethyleneamino)phenoxyl] ethoxy}-p-terf-butylcalix[4]arene(CompoundE),25,27-dihydroxy-26,28-bis{2-[2-(N-2-methyl-4-(2-methylazobenzene)phenylmethyleneamino)phenoxyl]ethoxy}-p-terT- butylcalix[4]arene(CompoundF),25,27-dihydroxy-26,28-bis{2-[2-(N-4-azobenzene-α-naphthylmethyleneamino)phenoxyl]ethoxy}-p-tert-butylcalix[4]arene(CompoundG ),25,27-dihydroxy-26,28-bis{2-[2-(N-4-(2-methylazobenzene)-α-naphthylmethylene amino)phenoxyl]ethoxy}-p-tert-butylcalix[4]arene (Compound H) and 25,27-dihydroxy-26,28-bis{2-[2-(N-4-(4-methylazobenzene)-α-naphthylmethyleneamino) phenoxyl]ethoxy}-p-tert-butylcalix[4]arene (Compound Ⅰ). The orthogonal experiment was used to optimize the synthesis of Compound E and improve the yield from 62.7% to 79.4%.④ Compound D reacted with 3,2’-dimethyl-4-aminoazobenzene to form 25,27-dihydroxy-26,28-bis{2-[4-(N-2-methyl-4-(2-methylazobenzene)phenylmethyle neamino)phenoxyl]ethoxy}-p-tert-butylcalix[4]arene(CompoundJ).⑤ All of the products are characterized by IR,1H-NMR and Elemental Analysis.⑥ The recognition of Compound E, Compound F, Compound G, Compound H and Compound I up metal ions were investigated mainly by UV-vis spectra. The result show that Compound H and Compound Ⅰ has a remarkable red shift when only added Al3+ among the ions dectected.The fourth chapter is the conclusion of the paper and discussion of further work.