Syntheses And Properties Of Novel Calixarene Aza-derivatives And Thiacalix[4]Arene

Calixarenes are macrocylic compounds generally formed by condensation of aldehydesand substituted phenols. Because calixarenes have a calix-shaped, hydrophobic cavity andseveral reactable positions, they have attracted considerable attentions. They are broadlyused as building blocks to construct well preorganized host molecules which have widelyapplying potential in the field of molecular recognition, enzyme mimics, etc. So they areconsidered as the third host molecule after crown ethers and cyclodextrins insupramolecular chemistry. In this thesis, the novel thiacalix[4]arene - based polymers andcalix[4]-aza, thio-crowns were designed, synthesized and their complexation propertieswere studied. Some meaningful results were obtained.Firstly, a series of new calix[4]arene derivatives were synthesized. It was found thatthey not only possessed good complexation properties for both soft and hard cations, butalso exhibited good complexation selectivity for Na~+and Ag~+. Secondly, thiacalix[4]arenebi-benzaldehyde derivative was synthesized by introducing benzaldehyde groups on1,3-position of p-tert-butylthiacalix[4]arene. Reacting compound with aniline, salicylichydrazide, nicotinic hydrazide or isonicotinic hydrazide gave series of novelthiacalix[4]arene aza derivatives by the Schiff-base condensation in the yields of 83%,80%, 77% and 79%, respectively. Treatment compound with o-phenylendiamine, oxalyldihydrazide, malonic dihydrazide and adipie dihydrazide, afforded novel bridgedthiacalix[4]arene aza derivatives by "1+1" condensation in the yields of 53%, 51%, 59%and 66%. The structures of all new compounds were characterized by IR, ESI-MS, ~1HNMR spectra and elemental analyses. At last, the first example of bisealixarene composedof calix[4]arene and thiacalix[4]arene subunits was facilely synthesized and showed goodcomplexation properties for metal cations and zwitterionieα-amino acids.