Synthesis of calixcrown oxime derivatives containing oxygen or sulphur oxime and their usage in liguid-liguid extraction studies

ABSTRACTMs. Sci ThesisSynthesis of calixcrown oxime derivatives containing oxygen or sulphur oximeand Their Usage in liquid-liquid extraction studies.Selma ASLANAfyonkarahisar Kocatepe UniversityFaculty of Science and ArtsDepartment of ChemistrySupervisor: Yrd. Doç. Dr. Gülderen Uysal AKKUŞThe study comprises synthesis of kaliks[4]-(oxa)-crown-4 and kaliks[4]-(tiya)-crown-4compounds and their corresponding oxime derivatives as well as the liquid-liquidextraction studies of these compounds.Structures of these compounds were characterized by spectroscopic techniques (FTIR,Mass, 1H NMR) and elemental analysis.Synthetic work was carried out according to the methods described elsewhere. Afterthe synthesis of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra-hydroxycalix[4]-arene 1, asolution of this compound in benzene in the presence of K+-tert-butokside was treatedwith triethylene glycol di-p-tosylate to obtain p-tert-butylcalix[4]-crown-4 (5) andtreated with 1,8-ditosylato-3,6-dithiaoctane to obtain p-tert-butylcalix[4]-thia-crown-4(6) respectively. Nitrile derivatives (4,5) were obtained by treatment of thesecompounds with 4-chlorobutyronitrile in dry acetonitrile in the presence of K2CO3 andNaI.Then nitrile groups in these compounds were reduced to amino groups (6,7) bytreatment of these compounds with LiAlH4 in dry THF. Then vic-dioxime derivativesof calix[4]arenes (8,9) were synthesized by treatment of these compounds with amphi-chloromonooxime in methanol-THF. Liquid-liquid extraction studies of all of thesecompounds were performed with some selected alkali (Na+, K+ ve Cs+) and transitionmetal (Cu2+, Co2+, Ni2+, Cd2+ and Hg2+) cations.2007, 71 pagesKeywords: calix[4]arene, calixcrown, calix-oxime, ion exchange, liquid-liquidextraction