Functionalized Resorcinol Calixarene Host Molecule Design, Synthesis And Applications

Calix[4]resorcinarenes represent an important class of synthetic host moleculesand have versatile applications in supramolecule chemistry, crystal engineering aswell as many other fields. We initiated the studies concerning the molecular design,syntheses and molecular recognition properties of some kinds of factionalcalix[4]resorcinarene derivatives, making a series of significant and creative resultsand developments. The main interesting results are as follows:1. We totally synthesized fifty-four new calix[4]resorcinarene derivatives, includingesters, allyl ethers, amides, Schiff bases, glycosides, thiourea derivatives. Besidescharacterizing their structures by NMR and IR, Uv-vis. the single crystal structureof one representative ester was determined by X-raydiffraction method.2. We systematically developed three routes of the preparation of calix[4]resorcinarene amide derivatives, which are directly amidination of calix[4]resorcinarene esters with amines including moni- and diamines; amidination of calix[4]resorcinarene acyl chloride with amines; direct alkylation of phenolic hydroxyl groups of calix[4]resorcinarene with chloroacetoamides.3. A series of polydentate Schiff base ligands of calix[4]resorcinarene were easily prepared from the amides which containing terminal amino groups with salicylaldehyde. From the reactions of this kind of amides with phenyl isothiocyanate or glycosyl isothiocyanate, some calix[4]resorcinarene thiourea derivatives were also obtained in high yields.4. From the successfully amidination reaction of diamine, or amidination of diethanolamine or trihydroxymethylamine, Michael addition of methyl acrylate and condensation with saliclylaldehyde, the arbrol and polyamidoamine types of calix[4]resorcinarenes core dendrimers were prepared. The third generation of dendrimers contains mostly 48 terminal long chain salicylideneimine groups.5. The applications in extraction, recognition, determination of several representative calix[4]resorcinarene derivatives for metal ions or anions were, investigated with the use of UV-vis spectrometry and atomic absorption spectrometry. The relationship of molecular structure of calixarene with analytical selectivity was prelimarily summed.