Synthesis And Property Of Azo-calix[4] Arene Derivatives Containg Modrphlen Unit

Calixarene are considered as the third generation supramolecular hosters after cyclodextrins and crown ethers. Tetrahydroxycalix[4]arene as basic molecular scaffolds of host-guest chemistry and their potential applications in supramolecular chemistry have been received much attention such as coordination chemistry, molecular recognition, supramolecular self-assembly,molecular devices, chemical sensors, liquid crystal and nanomaterials.Major works in this paper: series of azo-calix[4]arene derivatives modified morpholine were designed and synthesized. Theie complexation properties with metal ions were studied by UV-visible spectroscopy. The results are as follows:(1) 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix[4]arene was synthesized from p-tert-butylphenol and formaldehyde, which was used to synthesize25,26,27,28-tetrahydroxycalix[4]arene.(2) 25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene were synthesized from 25,26,27,28-tetrahydroxycalix[4]arene.(3) 25,27-bis[(2-N,N-diethyl-dithiocarbamoyl)ethoxy]-26,28-dihydroxycalix[4] -arene; 25,27-bis[2-(8-oxyquinoline)ethoxy]-26,28-dihydroxycalix[4]arene; 25-[2-(N-morpholine)ethoxy]-27-(2-bromoethoxy)-26,28-dihydroxycalix[4]arene and 25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene were synthesized from 25,27- bis(2-bromoethoxy)-26,28- dihydroxycalix[4]arene.(4) A series of azocalix[4]arene derivatives were synthesized: 5,17-diphenylazo-25,27-bis[2-(N,N-diethyl-dithiocarbamoyl)ethoxy]-26,28-dihydroxycalix[4]arene;5,17-diphenylazo-25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene;5,17-di(2-methylphenyl)azo-25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene;5,17-di(4-methylphenyl)azo-25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene;5,17-di(4-nitrophenyl)azo-25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene.(5) Besides 1H NMR and IR dentification of all these calix[4]arenas and ESI-MS single-crystal X-ray analysis dentification of some. The reaction yield of 25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene was improved by the orthogonal experiment.(6) The complexation properties with metal ions of azocalix[4]arene derivatives modified morpholine were studied by UV-visible spectroscopy. Especially 5,17-(4-nitrophenyl)azo-25,27-bis[2-(N-morpholine)ethoxy]-26,28-dihydroxycalix[4]arene displayed very high selectivity for Ca2+ , which leads to an obvious color changes from yellow to purple detected by the naked eye.