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

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

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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: [phone]; e-mail: [e-mail]].

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