Solvent Extractions of Alkali Metal Cations and Alkaline Earth Cations by Ionizable Crown Ether Phosphonic Acids

이온성 크라운에테르 포스포닉산에 의한 알칼리 금속 양이온과 알칼리 토금속 양이온의 용매추출

  • Chung, Yeong-Jin (School of Fire & Disaster Prevention, Samcheok National University)
  • 정연진 (삼척대학교 소방방재학부)
  • Published : 2005.03.31


A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of $Na^+$ and $Ca^{2+}$ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{3}$. As the result, $Na^+$ and $Ca^{2+}$ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{4}$was found to be somewhat selective for $Na^+$ over $Li^+$ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid $\underline{4}$, $Ca^{2+}$ and $Sr^{2+}$ are the appropriate sizes, but lager $Ba^{2+}$ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.



  1. C. J. Pedersen, Ionic Complexes of Macrocyclic Polyethers, Fed. Proc., Fed. Am. Soc. Exp. Biol., 27, 1305 (1968)
  2. M. Hiroaka, 'Crown Compounds-Their Characteristics and Applications', Kodansha Ltd., Tokyo (1982)
  3. W. Walkowiak, W. A. Charewicz, S. I. Kang, I. W. Yang, M. J. Pugia, and R. A. Bartsch, Effect of Structural Variations within Lipophilic Dibenzocrown Ether Carboxylic Acids on the Selectivity and Efficciency of Competitive Alkali-Metal Cation Solvent Extraction into Chloroform, Anal. Chem. 62, 2018 (1990)
  4. Y. Katayama, K. Ueda, H. Nakamura, and M. Tagagi, Synthesis of Chromogenic Crown Ethers and Liquid-Liquid Extraction of Alkali Metal Ions, Anal. Chim. Acta, 173, 193 (1985)
  5. M. Tazagi, K. Nita, M. Takagi, and K. Ueno, Carboxymethyl and Phosphonomethyl Derivatives of Aza-crown Ethers, Chem. Lett., 571 (1982)
  6. N. Barakat, M. Burgard, Z. Asfari, J. Vicens, G. Montabon, and G. Duplatre, Solvent Extraction of Alkaline-Earth Ions by Dicarboxylated Calix[4]arens, Polyhedron, 17, 3649 (1998)
  7. S. Elshani, E. Kobzar, and R. A. Bartsch, Macrocyclic Ligands with Partially Fluorinated Sidearms : Synthesis and Metal Ion Complexation, Tetrahedron, 56, 3291 (2000)
  8. S. Williams, S. M. Blair, J. S. Brodbelt, X. Huang, and R. A. Bartsch, Determination of Alkali Metal Cation Selectivities of Dibenzo-16-Crown-5 Lariat Ehers with Ether Pendant Group by Using Elecrospray Ionization Quadruplole Ion Trap Mass Spectromery, Int. J. Mass Spectrom, 212, 389 (2001)
  9. S. M. Williams, J. S. Brodbelt, and R. A. Bartsch, Evaluation of Alkali and Alkaline Earth Metal Cation Selectives of Lariat Ether Amides by Electrospray Ionization Mass Spectrometry, J. Am Soc. Mass Spectrom, 14, 1215 (2003)
  10. R. A. Bartsch, Y. Liu, S. I. Kang, B. -K. Son, G. S. Reo, P. G. Hipes, and L. J. Bills, Synthesis of Highly Liphophilic Crown Ether Carboxylic Acids, J. Org. Chem., 48, 4864 (1983)
  11. J. F. Koszuk, B. P. Czech, W. Walkowiak, D. A. Babb, and R. A. Bartsch, Lipophilic Crown Phosphonic Acid Monoalkyl Esters. Synthesis and Solvent Extraction, J. Chem. Soc., Chem. Commun., 1504 (1984)
  12. M. J. Pugia, G. Nidip, H. K. Lee, I. W. Yang, and R. A. Bartsch, Competitive Solvent Exreaction of Alkali Metal Cations into Chloroform by Lipophilic Crown Ether Phosphonic Acid Monoethyl Esters, Anal. Chem. 58, 2723 (1986)
  13. Y. J. Chung, Competitive Solvent Extraction of Alkaline Earth Metal Cations by Crown Ether Phosphonic Acid Monoethyl Esters, J. Kor. Oil Chem. Soc. 22(1) in press (2004)
  14. R. D. Shannon, Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides, Acta cryst., A32, 751 (1976)
  15. R. D. Shannon and C. T. Prewitt, Effective Ionic Radii in Oxides and Fluorides, Acta cryst., 1325, 925 (1969)

Cited by

  1. 크라운에테르 카르복시산과 크라운에테르 포스포닉산을 포함한 알칼리 금속과 알칼리 토금속 양이온 혼합물의 경쟁적 용매추출 vol.22, pp.3, 2005,