Hydrophobic Concave Surfaces and Cavities by Combination of Calix[4]arenes and Resorcin[4]arenes

作者：Peter Timmerman, Klaas G.J. Nierop, Erik A. Brinks, Willem Verboom, Frank C. J. M. van Veggel, Willem P. van Hoorn, David N. Reinhoudt · 发表于：Chemistry - A European Journal · 年份：1995 · DOI：10.1002/chem.19950010207 · 被引用次数：61 · 研究领域：Supramolecular Chemistry and Complexes、Methane Hydrates and Related Phenomena、Mass Spectrometry Techniques and Applications

Abstract Coupling reactions of calix[4]arenes and modified resorcin[4]arenes have been investigated. Reaction of mono(chloroacetamido)calix[4]arene 4 with tetrahydroxycavitand 9 gave the 1:1 coupled product 13 in 61% yield. Combination of upper‐rim 1,3‐difunctionalized calix[4]arene 5 with 9 afforded predominantly the 2:1 calix‐resorcinarene 18 in 47% yield. Reaction of 1,2‐difunctionalized calix[4]arene 6 with 9 gave five products, namely, endo 1:1 (19), exo 1:1 (20), endo‐endo 2:1 (21), endo‐exo 2:1 (22), and exo‐exo 2:1 (23) in ratios that depend on the reaction conditions. The stereochemistry of the different products was determined with NOESY experiments. The structures of 21 a and 23 b were calculated by using molecular mechanics, which revealed that intramolecular hydrogen bonds are only present in the former. Reaction of 1,2‐bis(chloroacetamido)calix[4]arene 26, which has two additional nitro groups at the remaining aromatic rings, with 9 yielded three different products, namely, endo 1:1 (28), endo‐endo 2:1 (30), and endo‐exo 2:1 (32) in ratios that depend on the reaction conditions. There is a preference for the endo orientation in the formation of the 1:1 coupled product, probably owing to an interaction of the nitro groups with the cavitand in the transition state. After conversion of the nitro groups in 28 into chloroacetamido moieties, reaction with Cs2CO3 in DMF under high‐dilution conditions afforded holand 33 in 26% yield together with calix[4]arene‐based car...