Design And Synthesis Of Thiol And Thioether Calixarene Derivatives

Calixarene is the third generation of supramolecules after crownether and cyclodextrin. The cavity size of calixarene can be adjusted by changing the number of the phenol monocase. The conformation of the calixarene is instable but can be controlled and the brim can be modified by adding function group. Now it has been applied widely in many domains,such as molecular recognition, chemical sensor, molecular assembly, optoelectronic, nano material and so on. Sulfur compounds, especially sulfhydryl(-SH) compounds, have a strong coordination ability, so it can form a monomolecular film in the surface of many precious metals. Therefore, these substances enjoy high favor among the chemical and material scientists in the self-assembled monolayer (Self-Assembled Monolayers, SAMs) research.Thiacalixarene is one kind of calixarene in which bridged methylene replaced by sulfur bond. Comparing with the classic calixarenes, thiacalixarene has different complex ability to transition metals, different conformational preferences and the three-dimensional configuration, because of this kind of replacement. In order to investigate the calixarene cavity size, arm length, and function of the number of machines on the impact of self-assembly, we studied the synthesis of calixarene-based dendrimers and used thiacalix[4]arene as the platform for the synthesis of arylthioether. We hoped it could have some novel properties in molecular recognition,multiple recognition and self-assembly. The synthesis result of this paper as follows:1. Thiol functional groups with calix[4]arene Derivatives: 4-tert-butylphenol in barium hydroxide, barium oxide and sodium hydride as base, DMF as solvent under conditions to generate targeted calix[4]arene, and then protection of certain basic conditions of the three calixarene hydroxyl and the lower edge of intermediate products obtained by synthesis of disulfides, the two calixarene molecules able to link by the two sulfur functional groups, and finally succeeded through the reduction reaction synthesized with thiol functional group of the calix[4]arene derivatives.2. Thiol functional groups with calix[6]arene Derivatives: 4-tert-butylphenol under alkaline conditions in high yields by one-step synthesis of calix[6]arene, and then THF / K2CO3 system for the synthesis out with a single substituted calix[6]arene derivatives, then the synthesis of disulfides, the two calixarene molecules able to link by the two sulfur functional groups, and finally successfully synthesized through the reduction of the thiol functional group with calix[6]arene derivatives.3. Functional group with methylthio thiacalix[4]arene derivatives: 4-tert-butylphenol under alkaline conditions in high yields by one-step synthesis of a thiacalix[4]arene, and then in particular Under alkaline conditions the protection of the base through the use of reasonable synthetic strategy conformation, some thia scale calixarene precursor molecules. Also carried out functional groups containing methylthio-end block the synthesis of molecules, and finally it through Sonogashira coupling and Suzuki coupling reaction of aromatics and sulfur complex coupling precursor molecules synthesized with functional groups methylthio sulfur complex thiacalix[4]arene derivatives.