Collect. Czech. Chem. Commun. 2004, 69, 1009-1026

Selective Derivatization of Calix[4]arenes via Amino Groups Attached to the Wide Rim

Anca Bogdan, Myroslav O. Vysotsky and Volker Böhmer*

Fachbereich Chemie und Pharmazie, Abteilung Lehramt Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, D-55099 Mainz, Germany


A new strategy is proposed for the synthesis of tetraether derivatives of calix[4]arenes bearing at the wide rim nitro and phthalimido groups in well defined positions. Since both groups are precursors of amino functions, calix[4]arenes substituted by different N-acylamino residues are easily available in four steps. The essential steps during the synthesis of the precursor consist in the protection of amino groups by the formation of their phthalimides followed by ipso-nitration of the remaining tert-butylphenol ether units. This nitration occurs without side reactions at the phthalimido substituted units, in contrast to simple N-acyl derivatives.

Keywords: Acylations; Calixarenes; ipso-Nitration; Hydrogenation; Regioselectivity; Nitro compounds; Amines; Anilines; NMR spectroscopy.

References: 61 live references.