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Synthesis 2008(18): 2968-2976  
DOI: 10.1055/s-2008-1067250
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Convenient Preparation of C-Silylated Calixarenes

Paul F. Hudrlik*, Anne M. Hudrlik, Wondwossen D. Arasho, Raymond J. Butcher
Department of Chemistry, Howard University, Washington, DC 20059, USA
Fax: +1(202)8065442; e-Mail: phudrlik@howard.edu;
Further Information

Publication History

Received 20 March 2008
Publication Date:
04 September 2008 (online)

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Abstract

Calix[4]arenes having multiple silyl groups on the upper (wide) rim were prepared from the corresponding bromocalixarenes by halogen-metal exchange with t-BuLi followed by silylation. The best results were obtained using the clear supernatant from a mixture of chlorosilane and triethylamine. With the higher molecular weight chlorosilanes, an aqueous workup was replaced by a filtration through a column of silica gel. p-(Trimethylsilyl)calixarene 17, the silicon analogue of the well-studied p-tert-butylcalixarene 1, formed a crystalline complex with toluene having a toluene molecule in the cone cavity with the toluene methyl protruding out at an angle.

Key words

calixarenes - silicon - halogen-metal exchange

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25

The cone assignments were confirmed by the appearance of ArCH 2Ar in the ¹H NMR spectra¹³,²6a (one pair of doublets at δ = 4.0-4.5 and 2.8-3.6; J = 13-14 Hz), and the position of the ArCH2Ar (δ = 31-32) in the ¹³C NMR spectra.²6

36

Crystallographic data (excluding structure factors) for the structure in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 658532. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.ac.UK).