Investigation of Metal Cation and Dichromate Anios Extraction Properties of Some Calix[4, 8]aren Derivatives

Öz

This work has been synthesized according to literature methods for compounds of calix[4]arene and calix[8]arene bearing 4-nitrobenzyloxy, 4-aminobenzyloxy and 3-aminopropyloxy groups. To view the ion transport properties of these compounds liquid-liquid extraction studies were performed with metal cations (K⁺, Na⁺, Cs⁺, Co²⁺, Cd²⁺, Ni²⁺, Cu²⁺, Hg²⁺, ve Pb²⁺) and  chromate ions. Extraction studies have shown that the amine group-containing calixarenes are large amounts in organic phase transport from the aqueous phase due to higher interaction with the metals than the nitro group-bearing calixarenes. In addition, it was observed that the 1 and 3 compounds carried Na₂Cr₂O₇ to a large extent from the aqueous phase to the organic phase at low pH.

Anahtar Kelimeler

• Calixarene,Toxic metal,Liquid-liquid extraction,Dichromate anions

Bazı Kaliks[4, 8]aren Türevlerinin Metal ve Kromat İyon Taşıma Özelliklerinin İncelenmesi

Öz

Bu çalışmada 4-nitrobenziloksi, 4-aminobenziloksi ve 3-aminopropiloksi grupları taşıyan kaliks[4]aren ve kaliks[8]aren bileşikleri literatür metotlara göre sentezlenmiştir. Bu bileşiklerin iyon taşıma özelliklerini görmek için sıvı-sıvı ekstraksiyon çalışmaları metal katyonları (K⁺, Na⁺, Cs⁺, Co²⁺, Cd²⁺, Ni²⁺, Cu²⁺, Hg²⁺, ve Pb²⁺) ve kromat iyonu ile yapılmıştır. Ekstraksiyon çalışmaları, amin grubu içeren kaliksarenlerin, nitro grubu taşıyan kaliksarenlere göre metallerle daha yüksek etkileşim yapmalarından dolayı sulu fazdan organik faza taşımasının daha fazla olduğunu göstermiştir. Ayrıca 1 ve 3 bileşiklerin Na₂Cr₂O₇’i düşük pH’larda büyük oranda sulu fazdan organik faza taşıdığı gözlenmiştir.

Anahtar Kelimeler

• Kaliksaren,Toksik metal,Sıvı-sıvı ektraksiyon,Dikromat anyonu

Kaynakça

1. [1] Antonio, M.T., Corredor, L., Leret, M. L. 2003. Study of the activity of several brain enzymes like markers of the neutrotoxicity induced by perinatal exposure to lead and/or cadmium. Toxicology Letters, 143 (2003), 331-340.
2. [2] Fels, L.M. 1999. Risk assessment of nephrotoxicity of cadmium. Renal Failure, 21, (1999), 275-281.
3. [3] Klassen, C.D., Amdur, M.D., Dull, J., 1986. Casarett and Doull’s Toxicology, 3rd ed., MacMillan, New Yorkİ 314s.
4. [4] Fergusson, J.E., 1990. Heavy Elements: Chemistry Environmental Impact and Health Effects, Pergamon Press, Oxford, 510s.
5. [5] Kaim, W., Schwederski, B. 1991. Bioinorganic Chemistry: Inorganic Elements in the Chemistry of life, an Introduction and Guide, WileyInterscience, New York, 335s.
6. [6] Tabakçı, M. 2006. Toksik anyon ve katyonlarin kaliksarenler kullanilarak nanofiltrasyon ve adsorpsiyon teknikleriyle giderilmesi. Selçuk Üniversitesi, Fen Bilimleri Enstitüsü, Doktora Tezi, 26s, Konya.
7. [7] Tabakci, M., Memon, S., Yilmaz, M., Roundhill, D.M., 2003. Synthesis and extraction studies of a versatile calix [4] arene-based “proton-switchable extractant” for toxic metals and dichromate anions. Journal of inclusion phenomena and macrocyclic chemistry, 45(3-4), 267-270.
8. [8] Böhmer, V., Vogt, W., Harris, S.J., Leonard, R.G., Collins, E.M., Deasy, M., McKervey, M.A., Owens, M., 1990. Selective monohydrolysis of a calix [4] arene tetraethyl ester with trifluoroacetic acid and its inhibition by Na+ ion: evidence for hydronium ion complexation. Journal of the Chemical Society, Perkin Transactions 1, (2), 431-432.

9. [9] Busch, D.H., 1993. The complete coordination chemistry-one practioner's perspective. Chemical reviews, 93(3), 847-860.
10. [10] Memon, S., Akceylan, E., Sap, B., Tabakci, M., Roundhill, D.M., Yilmaz, M., 2003. Polymer supported calix [4] arene derivatives for the extraction of metals and dichromate anions. Journal of Polymers and the Environment, 11(2), 67-74.
11. [11] Tabakci, M., Memon, S., Yilmaz, M., Roundhill, D.M., 2004. Synthesis and evaluation of extraction ability of calix [4]-crown-6 cone conformer and its oligomeric analogue. Reactive and Functional Polymers, 58(1), 27-34.
12. [12] Tabakci, M., Memon, S., Yilmaz, M., Roundhill, D.M., 2004. Oligomeric calix [4] arene‐thiacrown ether for toxic heavy metals. Journal of Polymer Science Part A: Polymer Chemistry, 42(1), 186-193.
13. [13] Erdemir, S., Deveci, P., Taner, B., Kocyigit, O. 2012. Synthesis and electrochemical properties of calix[4]arene derivatives containing ferrocene units in the cone and 1,3-alternate conformation. Tetrahedron. 68, (2012), 642-646.
14. [14] Güngör, Ö., Memon, S., Yılmaz, M., Roundhill, M.D. 2005. Synthesis of alkyl nitrile and alkyl benzonitrile derivatives of calix [4] arene and their polymer supported analogues: a comparative study in two-phase extraction systems. Reactive and Functional Polymers. 63, (2005), 1-9.
15. [15] Pedersen, C.J. 1968. Ionic complexes of macrocyclic polyethres, Federation Proceedings. 27, (1968), 1305–1309.
16. [16] Roundhill, D.M., 1995. Metal complexes of calixarenes. Kenneth D. K. (Ed.) In Progress in inorganic chemistry, s. 533-592.
17. [17] Yilmaz, M., Sayin, S., 2016. Calixarenes in organo and biomimetic catalysis. Neri, P., Sessler, J.L., Wang, M.X. (Eds.), In Calixarenes and Beyond s. 719-742.
18. [18] Kavallieratos, K., Moyer, B.A., 2001. Attenuation of Hofmeister bias in ion-pair extraction by a disulfonamide anion host used in strikingly effective synergistic combination with a calix-crown Cs+ host. Chemical Communications, (17), 1620-1621.