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DOI: 10.1039/A607259C (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 1193-1200

The first acid constant of calix[4]arenes

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Michaela Backes, Volker Böhmer, George Ferguson, Cordula Grüttner, Christian Schmidt, Walter Vogt and Kadija Ziat

Abstract

A series of calix[4]arenes containing a single p-nitrophenol unit (or two p-nitrophenol units) have been synthesized by fragment condensation. Their first acid constant (pKa1) has been determined in 2-methoxyethanol–water (9[hair space]:[hair space]1) by optical titration. Relative to the corresponding linear trimers with a p-nitrophenol in the middle, a decrease of pKa1 by 2.1 units or more is observed, which can be explained entirely by intramolecular hydrogen bonds stabilising the monoanion. In this way electron-withdrawing p-substituents in the opposite phenolic unit lead to a further decrease in pKa1, while a distortion of the cone conformation by m-methyl groups causes a slight increase. The structure of one calix[4]arene was further confirmed by single crystal X-ray analysis showing the molecule in the usual cone conformation.

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