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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

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    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.