Competitive Solvent Extractions of Alkaline Earth Metal Cations by Crown Ether Phosphonic Acid Monoethyl Esters

크라운에테르 포스포닉산 모노에틸 에스테르에 의한 알칼리 토금속 양이온의 경쟁 용매추출

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


Competitive solvent extraction of alkaline earth metal cations from water into organic solvent containing the carboxylic acid crown ether and analogous crown ether phosphonic acid monoethyl esters were investigated. sym-(n-Decyldibenzo)-16-crown-5xyacetic acid $\underline{1}$ and monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ are structurally identical except for the ionizable groups. Both of them provide similar extraction behavior in terms of efficiency and selectivity, but monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ showed higher alkaline earth metals loadings at acidic or neutral media. Monoethylsym-(n-octyldibenzo)-16-rown-5-oxymethylphosphonic acid $\underline{2}$ showed better selectivity and alkaline earth metals loading than did the analogous sym-(n-octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{6}$.



  1. C. J. Pedersen, Ionic Complexes of Macrocyclic Polyethers, Fed Proc., Fed Amer. Soc. Exp. Biol., 27, 1305 (1968)
  2. H. K. Frensdoff, Salts Complexes of Cyclic Polyethers. Distribution Equilibria, J. Amer. Chem. Soc., 93, 4684 (1971)
  3. A. Sadakane, T. Iwachido, and K. Toei, The Extraction of Alkali Metal Picrates with Dibenzo-18-Crown-6, Bull. Chem. Sac. Jpn, 48, 60 (1975)
  4. K. H. Pannell, W. Yee, G. S. Lewandos, and D. G. Hambrick, Electronic Substituent Effects upon the Selectivity of Synthetic Ionophores, J. Amer. Chem soc., 99, 1457 (1977)
  5. 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)
  6. S. Elshani, E. Kobzar, and R. A. Bartsch, Macrocyclic Ligands with Partially Fluorinated Sidearms : Synthesis and Metal Ion Complexation, Tetrahedron, 56, 3291 (2000)
  7. 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 Spectrometry, Inter. J. of Mass Spectrometry, 212, 389 (2001)
  8. S. M. Williams, J. S. Brodbelt, and R. A. Bartsch, Evaluation of Alkali and Alkaline Earth Metal Cation Selectives of Lariat Ether Arnides by Electrospray Ionization Mass Spectrometry, J. Amer. Soc. for Mass Spectrometry, 4, 1215 (2003)
  9. R. A. Bartsch, Y. Liu, S. I. Kang, B. -K. Son, G. S. Hea, P. G. Hipes, and L. J. Bills, Synthesis of Highly Liphophilic Crown Ether Carboxylic Acids, J. Org. Chem., 48, 4864 (1983)
  10. R. A. Bartsch, G. S. Heo, S. I. Kang, Y. Liu, and J. Strzelbicki, Synthesis and Acidity of Crown Ethers with Pendant Carboxylic Acid Groups, J. Org. Chem., 47, 457 (1982)
  11. 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)
  12. R. D. Shannon, Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides, Acta Cryst., A32, 751 (1976)
  13. R. D. Shannon and C. T. Prewitt, Effective Ionic Radii in Oxides and Fluorides, Acta cryst., 1325, 925 (1969)
  14. J. P. Shukla, E. G. Jeon, B. E. knudsen, M. J. Pugia, J. S. Bradshaw, and R. A. Bartsch, Thermodynamic Acid Dissociation Constants for Proton-Ionizable Crown Compounds in Aqueous Dioxane, Thermochimica Acta, 130, 103 (1988)
  15. S. I. Kang, 'Ionizable Crown Ether for the Separation of Alkali and Alkaline Earth Metal Cations Synthesis and Applications', Ph.D. Dissertation, Texas Tech University (1983)