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Synthesis, Conformations and Extraction Properties of New Chromogenic Calix[4]arene Amide Derivatives
Author(s) -
Halouani Hatem,
DumazetBonnamour Isabelle,
Duchamp Christian,
Bavoux Claude,
Ehlinger Noëlle,
Perrin Monique,
Lamartine Roger
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200212)2002:24<4202::aid-ejoc4202>3.0.co;2-q
Subject(s) - chemistry , chromogenic , calixarene , amide , extraction (chemistry) , combinatorial chemistry , stereochemistry , organic chemistry , chromatography , molecule
The synthesis of a new series of chromogenic calix[4]arene derivatives is described. p ‐Tetrakis(phenylazo)calix[4]arenes substituted with tertiary amide groups at the lower rim were obtained. The O ‐substitution of 25,26,27,28‐tetrahydroxy‐11,23‐bis(phenylazo)calix[4]arene ( 2 ) and 25,26,27,28‐tetrahydroxy‐5,17,11,23‐tetrakis(phenylazo)calix[4]arene ( 3 ) to provide 26,28‐bis{[(diethylamino)carbonyl]methoxy}‐25,27‐dihydroxy‐11,23‐bis(phenylazo)calix[4]arene ( 4 ), 26‐{[(diethylamino)carbonyl]methoxy}‐25,27,28‐trihydroxy5,11,17,23‐tetrakis(phenylazo)calix[4]arene ( 5 ), 25,26,27,28tetrakis{[(dialkylamino)carbonyl]methoxy}‐5,11,17,23tetrakis(phenylazo)calix[4]arene [alkyl = ethyl ( 6a ), methyl ( 7 )] and 26,28‐bis{[(diethylamino)carbonyl]methoxy}‐25,27‐dihydroxy‐5,11,17,23‐tetrakis(phenylazo)calix[4]arene ( 8a ) have been carried out by treatment of the precursors 2 and 3 with either α‐chloro‐ N , N ‐diethylacetamide or α‐chloro‐ N , N ‐dimethylacetamide. A potassium complex of 8 ( 8b ) was isolated. The structures of these compounds have been studied by NMR spectroscopy. In addition, the conformations have been confirmed by single‐crystal X‐ray analysis in the cases of tetra‐ O ‐substituted azocalix[4]arenes ( 6a and 7 ) and bis( O ‐substituted) azocalix[4]arenes ( 8a and 8b ). The resolved structures of 6a and 7 show 1,3‐alternate conformations while the bis( O ‐substituted) analogues 8 display cone conformations, their packing showing a zigzag chain of molecules for 8a and a dimer for 8b . Moreover, the extraction properties of 6a , 6b and 8a towards different metal ions have been studied by liquid‐liquid extraction and atomic absorption spectrometry and found to exhibit K + selectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2002)