Syntheses And Properties Study Of Ions Binding Calixarenes

In this paper, a series of upper-rim full substituted picolinoamidecalixarenes and full or part substituted calixarenes with pyridinylurea were synthesized, and their anions binding ability were also studied through UV-vis. The condensate of calixarene and polyether was also designed and synthesized. Phase-transfer ability of the oligomers was investigated in fluoridation.p-tert-Butylcaixarene experienced lower rim etherification, ipso-nitration, reduction, amidation to obtain 3 picolinoamide calix[4]arenes and 3 picolinoamide calix[6]arenes, which were characterized by 1H NMR, IR, MS. The complex of these compounds with anions and Cu2+ was investigated by UV-vis method. Picolinoamide calixarenes did not show any binding possibility with various anions, but revealed strong complex with Cu2+. The stoichiometric ratio of host and guest were 4:1 for the 6 compounds with Cu2+, and the binding constants were 25-90. 6 chlorobenzoylamide calixarenes were also synthesized here by the amidation of aminocalixarene. The structures were confirmed by 1H NMR, IR, MS. Meanwhile the UV-vis absorption of these compounds had no change after addition of different anions into their solvent.Pyridinylurea calixarenes were prepared by dealkalation, lower rim etherification, partial nitration, reduction and condensation from p-tert-butylcalixarenes. The new compounds were characterized by 1H NMR,IR,MS. The stoichiometric ratio 1:1 complexes were founded by UV-vis test. The binding constants were 2000-5000 between pyridinylurea calixarenes and terephthalic acid in DMSO. However, these structures revealed no binding potential to BF₄^- and CF₃SO₃^-, which often combined with N-fluoropyridinium.Phosphate calixarenes were reacted with PEG600 to obtain a condensate. The other two copolymers were synthesized through condensation between PEG600 and p-tert-calix[4]arene or p-tert-calix[6]arene. The 3 oligomers were characterized by, IR, 13C NMR,number average molecule-weight(vapor phase osmometry). In fluoridation, the two calix[4]arenes derivative showed phase-transfer catalysis ability fasting the reacting speed under the same reacting condition.