Study On Synthesis, Properties And Complexation Of P-tert-Butylcalix[n]arene Amide Derivatives

Calix[n]arene like crown ethers and cyclodextrms represent an important class of host in supraraolecular chemistry, which has two intrinsic feature including molecular recognition and self-assembly. During the past two decades, calix[n]arenes have become an very important framework in host-guest chemistry, which have versatile applications in crystal engineering as well as many other fields. We initiated the studies concerning the molecular design, syntheses of P-tert-butylcalix[n]dendrimers, making a series of significant and creative results and developments. The main interesting results are as follows:1. We totally synthesized several new p-tert-Buty\ca\ix[n]arene derivatives, including esters, allyl ethers, amides, Schiff bases,thiourea derivatives and calixarene organometallic compounds. Besides characterizing their structers by NMR and IR, Uv-vis. Two single crystal structure were determined by X-raydiffraction method.2. We synthesized a series p-tert-Butylcalix[n]arene amide derivatives, which are directly amidination of p-tert-Butylcalix[n]arene esters with amines including diamines, triethylene tetramine, hydroxylamine hydrochloride, trihydroxymethyl amine and so on.3. A series of polydentate Schiff base ligands ofp-fer/-Butylcalix[n]arene were prepared from the amides which containing terminal amino groups with aldehyde such as salicylaldehyde, pyridinecaldehyde, From the reactions of this kind of amides with glycosyl isothiocyanate to give thiourea derivatives.4. From the successfully amidination reaction of diamine, Michael addition of methyl acrylate and condensation with saliclylaldehyde, the arbrol and polyamidoamine types of p-terM3utylcalix[n]arene core dendrimers were prepared. The two generation of dendrimers contains mostly 16 terminal long chain salicylideneimine groups.5. Basic hydrolysis of the /7-tert-Butylcalix[n]arene esters gave quantitatively the /?-tert-Butylcalix[n]arene carboxylic acids. Besides the /?-terï¿¡-Butylcalix[n]arene esters can be selectively hydrolyzed by trifluoroaceticacid in chloroform to give the monoacid.6. A series of calixarene metal complexes were prepared from the />tert-Butylcalix[n]arene Schiff base or acylhydrone with metal acetates.