Thiacalix[4]arene derivatives as radium ionophores: A study on the requirements for Ra2+ extraction

Organic and Biomolecular Chemistry

Volumn 3, Issue 10, 2005, Pages 1993-2001

  Van Leeuwen, Fijs W B ^a   Beijleveld, Hans ^a   Velders, Aldrik H ^a   Huskens, Jurriaan ^a   Verboom, Willem ^a   Reinhoudt, David N ^a  

^a UNIVERSITY OF TWENTE   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACIDS; CROWN ETHERS; DERIVATIVES; EXTRACTION; IONOSPHERE; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

COVALENT COMBINATION; PENTADECANOIC ACID; RADIUM IONOPHORES; TETRACARBOXYLIC ACID;

RADIUM;

ARENE; STAPHYLOCOCCUS PHAGE 3A;

EID: 19944380843     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/b501587a     Document Type: Article

References (37)

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20. It seems that a difference in reactivity of the two hydroxyl groups of a thiacalix[4]crown allows for selective functionalization, a property that could be useful for the preparation of mixed substituent thiacalix[4]crowns.
21. 3 as a base (2 equiv). only gave partial conversion of thiacalix[4]crown-6 (1b) to the partial cone thiacalix[4]crown-6 monoester (11). This preferred formation of the partial cone 11 is rather surprizing, since a crown-5-ether bridge only allows for the formation of the monoester in the cone conformation 9.
22. All conformational assignments are fully confirmed by the complete NOESY data, including those of the t-butyl group resonances.
23. 1H NMR spectra of 7 the ArH1 and ArH3 peaks perfectly overlap.
24. The ArH3 NOE interaction with the crown-ether bridge allows assignment of the low field peaks to ArH2a/ArH4a and as a consequence the upfield peaks as ArH2b/ArH4b.
25. N. Iki, N. Morohashi, F. Narumi, T. Fujimoto, T. Suzuki and S. Miyano, Tetrahedron Lett., 1999, 40, 7337-7341.
26. Due to the sharper OH resonance found for the thiacalix[4]arene tricarboxylic ester (15), with respect to the corresponding thiacalix[4]arene tricarboxylic acid (7), compound 15 was used to assign their conformation.
27. 2+ were used as competing cations in this work.
28. R. D. Shannon, Acta Crystallogr., Sect. A, 1976, 32, 751-767.
29. 1H NMR spectroscopy after extraction with a tris-HCL buffer of pH 8.9. Furthermore, clear organic/aqueous phase separation was obtained after the extraction experiments.
30. 2+ extraction under the conditions studied.
31. -3 M) a third phase was observed with these ionophores.
32. 2+ were not determined.
33. 2+ salts does not influence the selectivity coefficients obtained and as such is not discussed.
34. 2+ extraction constants.
35. Partial cone thiacalix[4]crown-6 monocarboxylic acid (5) shows NOE cross peaks between the t-butyl3 resonances of the inversed aromatic unit of the thiacalix[4]arene and the crown-ether bridge, while its [Ba(5)Pic] complex does not. Nonetheless, NOE interactions between the resonances of the methylene group adjacent to the carboxylic acid moiety and ArH2 and ArH4 (strong) and t-butyl2 and t-butyl4 (weak) resonances, still confirm the partial cone conformation. Furthermore, the ArH2b and ArH4b peaks shift down field significantly (0.3 ppm) for the [Ba(5)Pic] complex. These NMR data suggest outward rotation of the t-butyl1 peak, to allow for inward rotation of the carboxylic acid group. To the best of our knowledge this is the first example that in the partial cone conformation a carboxylic acid moiety rotates into the cavity to interact with a cation at the other side of the thiacalix[4]arene platform (see ESI†).
36. G. G. Talanova, H.-S. Hwang, V. S. Talanov and R. A. Bartsch, Chem. Commun., 1998, 419-420.
37. 88Sr.