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Synthesis 1995; 1995(9): 1089-1096
DOI: 10.1055/s-1995-4075
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Selective Arylmethylation, Arylmethenylation and Aroylation of Mono- and Tetra-p-Cyanomethylcalix[4]arene

Shiv Kumar Sharma, Iftikhar Alam, C. David Gutsche*
  • *Department of Chemistry, Texas Christian University, Fort Worth, Texas 76129, USA, Fax +1(817)9217110
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Publication Date:
31 December 2000 (online)

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Tetra-p-cyanomethylcalix[4]arene (3) is selectively converted to its tetrabenzyl ethers 4 (1,3-alternate conformer) and 1,3-dibenzyl ethers 5 (cone conformer) by reaction with benzyl halides in the presence of variable amounts of potassium carbonate. Mono-p-cyanomethylcalix[4]arene (6) gives exclusively the cone conformer of the 1,3-disubstituted product 7 (benzyl moiety attached to the unsubstituted rings). Aroylation of 6 in the presence of sodium hydride gives tetrasubstituted product 9, whereas with aluminum chloride it produces an easily separable mixture of 1,3-disubstituted compounds 10 and 11. Surprisingly, no regioselectivity is achieved using 1-methylimidazole as the base. On the other hand, 6 reacts with 4-bromobenzenesulfonyl chloride under the same reaction conditions to produce the cone conformer of the tetrasubstituted product 12. Reactions of 6 with benzyl halides or benzaldehydes using sodium hydride as a base give the fully benzylated compounds 8 or the benzal derivatives 13, respectively.

p-cyanomethylcalix[4]arene - selective arylmethylation and arylmethenylation - aroylation