Study On Synthesis Of Functionalized Nitrogen-containing P-tert-Butylthiacalixarenes

Thiacalixarene is the new member of the calixarene host compounds which are considered as the third generation supermolecular hosters. It replaces the conventional calixarene methylene bridge with sulfur atoms. The presence of sulfur atoms not only makes the rigid structure and polarity of aromatic macrocycles have taken place in the larger change, but also makes thiacalixarene possess more outstanding features. Thiacalixarenes have much better metal complexing ability than the classical calixarene due to the bridging sulfur itself can take part in coordination, which is not existed in conventioanl calixarene. On the other hand, the different conformational preferences of thiacalixarene show more special complexation properties with metal ion. Therefore, we initialed the studies of the synthesis of the functioanlized nitrogen-containing thiacalix[4]arene derivatives with different conformation derivatives, and the complexing properties of the prepared ligands for transition metal ions. Some achieved interesting results were as follow.1、At first p-tert-butylthiacalix[4]arene was alkylated with methyl chloroacetate K2CO3/acetone to give thiacalixaryl acetate derivatives in cone, partial cone and1,3-alternate conformation. Then with subsquential reactions of hydrolysis, hydrazinolysis, condensation with phenyl isocyanate and phenyl isothiocyanate, a series of multi-conformational thiacalixarne derivative were efficiently synthesized. We also get some sulfonylcalixaiyl amine derivatives through the oxidation of sulfur bridge. Their structures were characterized by1H,13C NMR and IR spectroscopy, and confirmed by X-ray diffraction determination of several representative single crystals.2、p-tert-Butylthiacalix[4]arene was efficiently alkylated with four kinds of chloroalkoxy substituted aromatic aldehydes such as o-chloropropylvanillin, o-chlorobutylbenzaldehyde and p-chlorobutoxybenzaldehyde to give thiacalixarene monosubstituted and tetrasubstitutede derivatives. Then by condensation reactions with S-methyldithiocarbazate and S-benzyldithiocarbazate, thiosemicarbazide,2-,3-,4-pyridinecarbohydrazide, several kinds of functioanlized thiacalix[4]arene Schiff bases derivatives were obtained. Their structures were characterized by1H,13C NMR and IR spectroscopy.3、The compexing proepties of the thiacalix[4]arene Schiff bases for transition metal ions were studied with UV-vis spectroscopy. The results showed that Schiff bases have distinct selectivities for transition and heavy metal ions, specially for Zn2+、Cu2+、 Ni2+.