Synthesis Of Inherently Chiral Calix[4] Arenes

Inherently chiral calix[4]arenes are a typical chiral macrocyclic compounds in which chirality generated from the asymmetric arrangement of non-chiral substituents free from a chiral axis, a center chiral or a planar chiral molecules and other chiral factors. Calixarenes is an excellent molecular skeleton because of the rich derivatives spot, the flexible conformation and the variable size. The progress in inherently calix[4]arenes was summarized in the thesis. These compounds based on calixarene skeleton were found remarkable applications in the complexation extraction, molecular devices, molecular probes, film transfer, molecular swith, asymmetric catalysis and other fields. So inherently chiral calixarenes are very important not only in the three-dimensional configuration but also in enantiomeric recognition.Based on calix[4]crown skeleton separately reacted to bromoacetonitrile, propargyl bromide or 1,2-dibromoethane to give the corresponding inherently chiral calix[4]arenes. The contents of this thesis mainly involved the following points:1. p-tert-Butyl-calix[4]arene reacted with polyethylene glycol ditosylate to give 27,28-dihydroxy-p-tert-butyl-calix[4]-25,26-crowns.2. The reaction of 27,28-dihydroxy-p-tert-butyl-calix[4]-25,26-crowns with bromoacetonitrile, propargyl bromide or 1,2-dibromoethane in the presence of Potassium carbonate afforded 28-hydroxy-p-tert-butyl-25-substituted-calix[4]-26,27-crowns. The reaction condition was also optimized.3. The reaction of 25-propargylmethoxy-calix[4]-26,27-crowns with azides afforded 25-[(1H-1,2,3-trizol-4-yl)methoxy]-28-hydroxy-p-tert-butyl-calix[4]-26,27-crowns with unique chiral cavity structures by click reaction, and their metal ion recognition performance was studied.4. 12 new compounds were synthesized in this thesis, their structures were elucidated on the basis of IR, NMR, MS, HR-MS.5. Mg2+, Ca2+, Ni2+, Zn2+, Cu2+, Na+and Pb2+ were tested to evaluate the metal ion binding properties with 25-substituted-28-hydroxy-p-tert-butyl-calix[4]-26,27-crowns by UV and fluorescence spectra. Recognition toward glycine was also tested. Some good results were achieved.