Synthesis of Cyclic Calix-crown Derivatives and Using in the Phase-Transfer Reactions

Year 2014, Volume: 14 Issue: 1, 1 - 6, 01.04.2014

Gülderen Uysal Akkuş Emel Karaoğul Öz

Abstract

This study comprises synthesis of calixcrown derivatives containing cyclic structure that are selective extractants for toxic metal cations and their liquid-liquid extraction studies. Structures of these compounds were characterized by spectroscopic techniques (FTIR, H NMR, MAS) and elemental analysis. Synthetic work was carried out according to the methods described in the literature. After the synthesis of 5,11,17,23-tetra-ter-butyl-25,26,27,28-tetra-hydroxycalix[4]arene (1) ter-butyl groups on the p-position were removed by treating this compound with phenol in toluene along with aluminum chloride. Then compound 3 was obtained by treating compound 2 with p-nitrobenzyl bromide in acetonitrile in the presence of K2CO3. Compound 4 and 5 were obtained by reacting with compound 3 with triethyleneglycol ditosylate and 1,8-diptosylate-3,6-dithiaoctane respectively with Cs2CO3 in dry acetonitrile. Then nitro groups of these compounds were reduced individually by treatment of these compounds with Raney-Ni in the mixture of ethylacetate and methanol along with hydrazine (6 and 7). The compound 6 and 7 were reacting with adipoylchloride along with pyridine in dry THF individually to obtain compound 8 and 9. To view the ion transport properties of these compounds liquid-liquid extraction studies were performed with alkali (Li+ , Na+ , K+ and Cs+) transition metal (Ni2+, Co2+, Cu2+, Cd2+ and Hg2+ , Pb2+) cations and Cr2O7=anion. From the extraction data it has been concluded that the

Keywords

“Calixarene”, “Transition metal”, “Calixcrown”, “Phasetransfer”, “Solvent extraction”

Halkalı Yapıdaki Kaliks-crown Türevlerinin Sentezi ve Faz-transfer Reaksiyonlarında Kullanılması

Abstract

Bu çalışma, toksik metal katyonlar ve anyonlar için seçimli ekstraktant olan yeni halkalı yapıya sahip kaliks-crown türevlerinin sentezlenmesini ve bu bileşiklerin sıvı-sıvı ekstraksiyon çalışmalarını içermektedir. Sentezlenen bileşiklerin yapıları spektroskopik teknikler (FTIR, 1H NMR, Kütle) ve element analizi ile aydınlatıldı. Sentez çalışmalarında, literatürde belirtilen metodlardan yararlanarak 5,11,17,23tetra-ter-bütil-25,26,27,28-tetrahidroksikaliks[4]aren 1 sentezlendikten sonra, bu bileşik toluenli ortamda alüminyum klorür beraberinde fenol ile etkileştirilerek p-köşesindeki ter-bütil grupları giderildi. Daha sonra asetonitrilin çözücü olduğu ortamda K2CO3 beraberinde p-nitrobenzil bromür ile etkileştirilerek bileşik (3) sentezlendi. Elde edilen 3 nolu bileşik Cs2CO3’lü ortamda asetonitrilin çözücü olarak kullanılmasıyla sırasıyla trietilenglikolditosilat ile etkileştirilerek 4 nolu bileşik, 1,8-ditosilato-3,6ditiyaoktan ile etkileştirilerek de 5 nolu bileşik elde edildi. Daha sonra 4 ve 5 nolu bileşiklerin yapılarındaki NO2 grupları susuz etil asetat ve metanol karışımı içerisinde Raney-Ni ile hidrazin beraberinde etkileştirilerek amino gruplarına indirgendi (6 ve 7). Elde edilen bu 6 ve 7 nolu bileşikler ayrı ayrı susuz THF içerisinde piridin beraberinde adipoil klorür ile etkileştirilerek 8 ve 9 bileşikleri elde edildi. Sentezlenen bileşiklerin iyon taşıma özelliklerini görmek için alkali (Li+ , Na+ , K+ ve Cs+) ve geçiş metallerinin (Ni2+, Co2+, Cu2+, Cd2+ ve Hg2+ , Pb2+) pikrat çözeltileri ve Cr2O7= ile sıvı-sıvı ekstraksiyon çalışmaları yapıldı. Ekstraksiyon çalışmalarından elde edilen sonuçlara göre 8 nolu bileşiğin Na metaline karşı seçici olduğu görülürken 9 nolu bileşiğin özellikle Hg katyonuna karşı seçici davrandığı görülmektedir. Ayrıca değişik pH’larda dikromat anyon ekstraksiyon çalışmalarından 6 nolu bileşiğin Na2CrO7' ı büyük oranlarda sulu fazdan organik faza taşıdığı gözlendi

Keywords

“Kaliksaren”, “Geçiş metal”, “Kalikscrown”, “Faz transfer”, “Çözücü ekstraksiyonu”

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