Synthesis And Property Research Of Azo Calix[4]arene Compounds

In recent years, the research of host-guest chemistry has been deepened, one of hot-points of that research region is functional modification and application of the calixarene, and one of research directions is that azo groups are induced upper rim of calixarenes.Azo calix[4]arene compounds were synthesized in the paper. 5,11,17,23-tetra- [(4-carboxyl-phenyl)-azo]-25,26,27,28-tetrahydroxycalix[4]arene, 5,17-di-[(2-carboxyl- phenyl)-azo]-25,26,27,28-tetrahydroxycalix[4]arene, 5,11,17–tri-[(2-carboxyl-phenyl)- azo]-25,26,27,28-tetrahydroxycalix[4]arene, 5-[(antipyne)-azo]-25,26,27,28–tetrahydro- xy-calix[4]arene, 5,17-di-[(1-naphthyl)-azo]-25,26,27,28-tetrahydroxycalix[4]arene, 5, 11,17,23-tetra-[(2-naphthyl)-azo]-25,26,27,28-tetrahydroxycalix[4]arene, 5,11,17,23- tetra-[(2,4,6-tri-chlorine)-azo]-25,26,27,28-tetrahydroxycalix[4]arene were synthesized by calix[4]arene and 4-aminobenzoic acid, 2-aminobenzoic acid, 4-aminoantipyrine, 2-aminobenzothiazole, 1-naphthylamine, 2-naphthylamine, 2,4,6-thichloroaniline through diazotization-coupling reactions. 25-hydro-26,27,28-tri-methoxycalix[4]arene and 25,27-dihydro-26,28-dimethoxycalix[4]arene were synthe- sized by calix[4]arene through methylation reaction. Then, 5-[(4-carboxyl-phenyl)-azo]- 25-hydro-26,27,28- trimethoxycalix[4]arene and 5-[(2-naphthyl)-azo]-25-hydro-26,27,28-trimethoxy-calix [4]arene were synthesized by 25-hydro-26,27,28-trimethoxycalix[4]arene and 4-amino- benzoic acid and 2-naphthylamine through diazotization-coupling reactions. The synthesis conditions of 25-hydro-26,27,28-trimethoxycalix[4]arene were optimized by orthogonal tests, to gain more higheer yield of the compound. The structures of these compounds have been confirmed by IR, ¹H-NMR.The property of azo calix[4]arene has been primarily researched . First the solubility of the compounds were tested. The key measures were the UV-Vis spectrums variation of the azo calix[4]arene compounds in different dissolvents and acid -alkaline degree, and metal ions recognitions such as transition metal ions Cu²⁺, Hg²⁺, Cr³⁺, heavy metal Pb²⁺, lanthanide metal La³⁺. At last, the liquid membrane transportation of p-tert-butyl- calix[4]arene, calix[4]arene, 25-hydro-26,27,28-trimethoxy calix[4] arene for alkali metal ions Na⁺ , K⁺, transition metal ions Cu²⁺, La³⁺, heavy metal ion Pb²⁺, and rare-scattered metal ion Tl⁺ were tested, and the transportation rules and affection factors were primary discussed.