Synthesis of Calixarene Derivatives and Research on the Chromatographic Performance of 25,27-bis-(3-methylthiadiazole Thioethyoxyl)-calixarene Stationary Phase
|Keywords||calixarene derivatives HPLC stationary phase separation mechanism|
The calixarene stationary phase is one of the most interested fields in calixarene chemistry. Since Zinke discovered calixarene in 1940s, the synthesis of calixarene was improved continuously and more calixarene derivatives, like calixcrowns, chiral calixarenes, heteroatom calixarenes and calix-polymers were obtained. And they were widely used in many fields now. In this thesis studied, the synthesis of some calixarene derivatives were optimized, and acquired good results. The calixarene stationary phase with diazole group was bonded on silica gel and applied on research of the chromatographic performance. Three contents were studied in this article:1. Some p-tert-butyl calixarene derivatives were synthesized:25,27-bis(bromoe-thyoxyl)-calixarene,25,27-bis(a-methylbenzylamine ethyoxyl)-calixarene,25-(etho-xycarbonyl methoxyl)-calixarene,25,27-bis(ethoxycarbonyl methoxyl)-calixarene,25-(Aminopropyl aminocarbonyl methoxyl)-calixarene, 1,3-[propyl-bis(aminocarbonyl meth-oxyl)]-calixarene, calixarene-1,2-crown-4 and 25,27-bis-(3-methylthiadiazole thioeth-yoxyl)-calixarene. And characterized by MS,’H NMR and HPLC. The process was improved and acquired good results.2. The 25,27-bis-(3-methylthiadiazole thioethyoxyl)-calixarene stationary phase was synthesized, and characterized by IR, TGA and EA. Founded that the it has high chemical stability and thermal stability. The bonded amout of that phase was 0.052 mmol/g, the Column efficiency was 9073 plates/m. The calixarene phase was used for 10 months and founded that the reduation of the colum efficiency was less than 9%, the relative standard deviations(RSDs) of retention times were less than 3%.3. The chromatographic performance was investigated by separation of aniline derivatives, PAHs and Benzoic acid derivatives, and was compared with commercially available reversed-phase C18. The result was that the Calixarene stationary phase exhibited different retention characteristics, and was governed by a multitude of interaction mechanisms. Besides hydrophobic interaction, there were p-p interaction, hydrogen bond interaction and inclusion complexing interaction.