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Synthesis 2006(17): 2903-2906  
DOI: 10.1055/s-2006-942515
PAPER
© Georg Thieme Verlag Stuttgart · New York

Convenient Synthesis of Biscalix[4]arene and Its Cesium Selectivity

Chuan-Ming Jina, Chengfeng Yeb, Brendan Twamleyb, Jean’ne M. Shreeve*b
a Hubei Key Laboratory of Bioanalytic Technique, Hubei Normal University, Huangshi, 435002, P. R. of China
b Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343, USA
e-Mail: jshreeve@uidaho.edu;
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Publication History

Received 29 March 2006
Publication Date:
25 July 2006 (online)

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Abstract

A convenient method for the preparation of biscalix[4]arenes was established. Using the system of acetonitrile-potassium carbonate sealed in a Schlenk tube at 100 °C allows facile syntheses of symmetric biscalix[4]arenes and 25,27-dibromoalkyl calix[4]arene. The latter can be tethered by another equivalent of calix[4]arene to furnish an unsymmetric biscalix[4]arene that exhibits superior selectivity for cesium.

Keywords

biscalix[4]arene - calix[4]semitube - selectivity - cesium ion

    References

  • 1a Gutsche CD. Calixarenes, In Monographs in Supramolecular Chemistry   Stoddart JF. Royal Society of Chemistry; Cambridge: 1989. 
    Google Scholar
  • 1b Gutsche CD. Calixarenes Revisited, In Monographs in Supramolecular Chemistry   Stoddart JF. Royal Society of Chemistry; Cambridge: 1998. 
    Google Scholar
  • 2a Casnati A. Pochini A. Ungaro R. Ugozzoli F. Arnaud F. Fanni S. Schwing MJ. Egberink RJM. Jong FD. Reinhoudt DN. J. Am. Chem. Soc.  1995,  117:  2767 
    CrossrefGoogle Scholar
  • 2b Kim SK. Lee SH. Lee JY. Lee JY. Bartsch RA. Kim JS. J. Am. Chem. Soc.  2004,  126:  16499 
    CrossrefGoogle Scholar
  • 3 Casnati A. Pochini A. Ungaro R. Bocchi C. Ugozzoli F. Egberink RJM. Struijk H. Lugtenberg R. Jong F. Reinhoudt DN. Chem. Eur. J.  1996,  2:  436 
    CrossrefGoogle Scholar
  • 4a Schmitt P. Beer PD. Drew MGB. Sheen PD. Angew. Chem., Int. Ed. Engl.  1997,  36:  1840 
    CrossrefGoogle Scholar
  • 4b Matthews SE. Schmitt P. Felix V. Drew MGB. Beer PD. J. Am. Chem. Soc.  2002,  124:  1341 
    CrossrefGoogle Scholar
  • 4c Matthews SE. Rees NH. Felix V. Drew MGB. Beer PD. Inorg. Chem.  2003,  42:  729 
    CrossrefGoogle Scholar
  • 5a Webber PRA. Cowley A. Drew MGB. Beer PD. Chem. Eur. J.  2003,  9:  2439 
    Google Scholar
  • 5b Webber PRA. Beer PD. J. Chem. Soc., Dalton Trans.  2003,  2249 
    Google Scholar
  • 6a Kerdpaiboon N. Tomapatanaget B. Chailapakul O. Tuntulani T. J. Org. Chem.  2005,  70:  4797 
    CrossrefGoogle Scholar
  • 6b Webber PRA. Beer PD. Chen GZ. Felix V. Drew MGB. J. Am. Chem. Soc.  2003,  125:  5774 
    CrossrefGoogle Scholar
  • 7 Tantrakarn K. Ratanatawanate C. Pinsuk T. Chailapakul O. Tuntulani T. Tetrahedron Lett.  2003,  44:  33 
    CrossrefGoogle Scholar
  • 8 Li ZT. Ji GZ. Zhao CX. Yuan SD. Ding H. Huang C. Du AL. Wei M. J. Org. Chem.  1999,  64:  3572 
    CrossrefGoogle Scholar
  • 9 Tomapatanaget B. Pulpoka B. Tuntulani T. Chem. Lett.  1998,  1037 
    CrossrefGoogle Scholar
  • 10a Nabeshima T. Saiki T. Sumitomo K. Akine S. Tetrahedron Lett.  2004,  45:  6761 
    CrossrefGoogle Scholar
  • 10b Nabeshima T. Saiki T. Sumitomo K. Akine S. Tetrahedron Lett.  2004,  45:  4719 
    CrossrefGoogle Scholar
  • 13a Ngola SM. Dougherty DA. J. Org. Chem.  1998,  63:  4566 
    CrossrefGoogle Scholar
  • 13b Gillard RE. Stoddart JF. White AJP. Williams BJ. Williams DJ. J. Org. Chem.  1996,  61:  4504 
    CrossrefGoogle Scholar
  • 14a Picrate extraction experiments: Pedersen CJ. Fed. Proc. Fed. Am. Soc. Expl. Biol.  1968,  27:  1305 
    Google Scholar
  • 14b

    Picrate extraction from H2O into CH2Cl2 was done by the following procedure: A 4 × 10-5 M solution of metal picrate in H2O (10 mL) and 4 × 10-4 M solution of biscalix[4]arene derivatives (10 mL) were mechanically shaken in a stoppered glass flask for 2 min. Then the mixture was magnetically stirred for further 30 min at r.t., and finally left standing for a complete phase separation. The concentration of picrate ion remaining in the aqueous phase was determined using UV-Vis spectrometry. The percentage extraction (%E) was calculated from the absorbance A of the aqueous phase measured at 357 nm using the following expression: %E = 100 × (A 0 - A)/A 0 , where A 0 is the absorbance of the aqueous phase of a blank experiment carried out without biscalix[4]arene derivatives and A is absorbance after extraction.
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CCDC 281739 contains the supplementary crystallographic data for this crystal. These data can be obtained free of charge via www.ccdc.cam.ac.uk [or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].

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SHELXTL: Sheldrick G. M.; Structure Determination Software Suite, v 6.10; Bruker AXS Inc.: Madison, WI, 2001.