Synthesis And Properties Of A New Alizarin Residue Substituted Calix[4]arene Derivative

In this paper,a series of alizarin residue substituted calix[4]arene derivative were designed and synthesized.The recognition of these compounds upon metal ions were investigated by UV-vis spectrum and fluorescence spectrum.The results are as follows:(1)5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix[4]arene(compound A)was synthesized from p-tert-butylphenol and formaldehyde by polymerization reaction and was further used to synthesize 25,26,27,28-tetrahydroxycalix[4]arene(compound B)with aluminium chloride by reverse Friedel-Crafts alkylation reaction.(2)By selective etherisation,compound A and compound B reacted with 1,2-dibromoethane to form 5,11,17,23-tetra-t-butyl-25(2-bromoethoxy)-26,27,28-trihydroxycalix[4]arene(compound C)and 5,11,17,23-tetra-t-butyl-25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(compound D)and 25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(compound E).(3)The target compounds 5,11,17,23-tert-butyl-25-[2-(2-hydroxyanthraquin-oneoxy)ethyoxyl]-26,27,28-trihydroxy-calix[4]arene(compound F),5,11,17,23-tert-butyl-25-[2-(2-hydr-oxyanthra-quinoneoxy)ethyoxyl]-27-(2-bromoethoxy)-26,28-dih ydroxy-calix[4]arene(compound G),5,11,17,23-tert-butyl-25,27-bis[2-(2-hydroxy-anthraquinoneoxy)ethyoxyl]-26,28-dihydroxy-cali-x[4]arene(compound H)and 25,27-bis[2-(2-hydroxy-anthraquinoneoxy)ethyoxyl]-26,28-dihydroxy-calix[4]arene(compound I)was synthesized by the respectively reaction of Alizarin with compound C,compound D and compound E.(4)The target compounds 5,11,17,23-tert-butyl-25-[2-(2-aminophenoxy)ethyoxyl]-27-(2-hydroxye-thoxyl)-26,28-bihydroxycalix[4]arene(compound J)and 5,11,17,23-tert-butyl-25-[2-(3-aminophen-oxy)ethyoxyl]-27-(2-hydroxye-thoxyl)-26,28-bihydroxycalix[4]arene(compound K)was synthesized by the respectively reaction of compound D with o-aminophenol and m-aminophenol.(5)All the compounds were characterized by 1H NMR and IR and all the targets compound were characterized by ESI-MS and 13C NMR.(6)The yields of 5,11,17,23-tert-butyl-25-[2-(2-aminophenoxy)ethyoxyl]-27-(2-hydroxyethoxyl)-26,28-bihydroxycalix[4]arene(compound J)was improved by the orthogo-nal experiment.(7)The recognition of these novel calix[4]arene derivatives upon metal ions were investigated by UV-vis spectrum and fluorescence spectrum.The results show that(compound F)can recognize Mg2+,Co2+,Ni2+,Cu2+ in the UV-vis spectrum,which leads to obvious color change from light yellow to orange red detected by naked eyes;and only recognize Mg2+ in the fluorescence spectrum,The band intensity at 594 nm was surprisingly increased from 200 to 600 followed in case of Mg2+.compound I has a good selectivity for La3+,Ni2+,Cu2+,which leads to obvious color change from light yellow to red detected by naked eyes,the result of UV spectrum and fluorescence was same.compound J has a good specific selectivity for La3+,the result of UV spectrum and fluorescence was same.