CALIXARENES: A VERSA TILE CLASS OF MACROCYCLIC COMPOUNDS

Transcription

1 CALIXARENES: A VERSA TILE CLASS OF MACROCYCLIC COMPOUNDS

2 TOPICS IN INCLUSION SCIENCE Series Editor: J. E. D. DAVIES, University of Lancaster, u.k. Editorial Board: J. L. ATWOOD, University of Alabama, U.S.A. T. IWAMOTO, University of Tokyo, Japan N. N. LI, UOP Inc., Illinois, U.S.A. J. LIPKOWSKI, Academy of Sciences, Warsaw, Poland D. D. MacNICOL, University of Glasgow, Scotland W. SAENGER, Free University Berlin, Germany VOLUME 3 The titles published in this series are listed at the end of this volume.

3 CALIXARENES: A VERSATILE CLASS OF MACRO CYCLIC COMPOUNDS Edited by J. VICENS Ecole Europeenne des Rautes Etudes des Industries Chimiques Strasbourg, France and V.BOHMER Johannes Gutenberg Universitiit Mainz, F.R. G. KLUWER ACADEMIC PUBLISHERS DORDRECHT / BOSTON / LONDON

4 Library of Congress Cataloging-in-Publication Data Cal ixarenes: a versatile class of macrocyclic compounds I edited by J. Vicens and V. Bohmer. p. cm. -- (Topics in inclusion science) Includes bibliographical references. ISBN-13: e-isbn-13: DOl: / Calixarenes. I. Vicens. J. II. Bohmer. V. III. Series. QD341.P5C '.632--dc CIP Published by Kluwer Academic Publishers, P.O. Box 17, 3300 AA Dordrecht, The Netherlands. Kluwer Academic Publishers incorporates the publishing programmes of D. Reidel, Martinus Nijhoff, Dr W. Junk and MTP Press. Sold and distributed in the U.SA. and Canada by Kluwer Academic Publishers, 101 Philip Drive, Norwell, MA 02061, U.S.A. In all other countries, sold and distributed by Kluwer Academic Publishers Group, P.O. Box 322, 3300 AH Dordrecht, The Netherlands. All Rights Reserved 1991 by Kluwer Academic Publishers Softcover reprint of the hardcover 1st edition 1991 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

5 Contents Preface xi PART ONE: HISTORY AND SYNTHESIS OF CALIXARENES C. D. GUTSCHE: Single Step Synthesis and Properties of Calixarenes 3 1. Introduction 3 2. Single Step Synthesis of Calixarenes Base-Induced Procedures Acid-Catalyzed Procedures Thermally Induced Procedures Synthesis of Functionalized Calixarenes Introduction of Substituents on the 'Lower Rim' of Phenol- Derived Calixarenes Ester and Ether Formation with Monofunctionalized Reagents Esterification and Etherification with Polyfunctionalized Reagents Introduction of Substituents on the 'Upper Rim' of Phenol- Derived Calixarenes Dealkylation of p-alkylcalixarenes Electrophilic Substitution Route p-claisen Rearrangement Route p-quinonemethide Route p-chloromethylation Route Introduction of Substituents at the 'Upper Rim' of Resorcinol- Derived Calixarenes Introduction of Functional Groups at the Methylene Bridges of Calixarenes Physical Properties of Calixarenes Melting Points Solubilities Spectral Properties of Calixarenes 27 v

6 vi CONTENTS Infrared Spectra Ultraviolet Spectra NMR Spectra Mass Spectra Conduding Comments 34 References 34 V. BOHMER and J. VICENS: Special Calixarenes, Synthesis and Properties Introduction Stepwise Synthesis of Calixarenes Fragment Condensation Selective Functionalization The First Acidity Constant of Calix[4]arenes Chiral Calix[4]arenes Bridged Calixarenes Double Calixarenes and Future Directions 59 References 61 PART TWO: X-RAY STRUCTURAL DATA ON CALIXARENE ARCHITECTURES M. PERRIN and D. OEHLER: Conformations of Calixarenes in the Crystalline State Introduction Conformations and Structures of Some Precursors Conformations of Calixarenes Introduction Conformations of Calix[4]arenes Calix[4]arenes with a Fourfold Axis Calix[4]arenes with Symmetry Planes Calix[4]arenes with a Twofold Axis Calix[4]arenes in the Cone Conformation with No Particular Symmetry Conformations ofcalix[5]arene<; Conformations of Calix[6]arenes Calix[6]arenes with Symmetry Planes Calix[6]arenes in the Centro symmetrical Conformation Conformations of Calix[7]arenes Conformations of Calix[8]arenes Calix[8]arenes with Mirror Planes Conclusion 82 References 84

7 CONTENTS vii G. D. ANDREETTI and F. UGOZZOLI: Inclusion Properties and Host-Guest Interactions of Calixarenes in the Solid State Introduction General Considerations Conformational Properties of Calixarenes in the Solid State Conformational Preferences in Functionalized Calixarenes Calix[4]arenes Calix[6]arenes Calix[8]arenes Calixarene Cavitands Metallocalixarenes Calixarene Based Cation Carriers and Receptors Molecular Inclusion of Neutral Molecules by Calixarenes Intramolecular Complexes of Calixarenes Cage Complexes Intermolecular Complexes Clathrates Theoretical Models for the Host-Guest Interactions 119 Acknowledgements 122 References 122 PART THREE: INCLUSION PROPERTIES OF CALIXARENES AND THEIR DERIVATIVES R. UNGARO and A. POCHINI: Calixarene-Based Cation Receptors and Carriers Introduction Calixarene Podands with Ether Chains Calixarene Podands with Ester and Amide Groups Calixcrowns and Calixspherands Ionizable Calixarene Ligands Concluding Remarks 144 Acknowledgements 145 References 145 M.-J. SCHWING and M. A. McKERVEY: Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations Introduction Calixarenes as Receptor Substructures Chemically Modified Calixarenes Complexation of Alkali Cations: Phase Transfer, Stability Constants, Selectivities, and Transport Calixarene Esters and Ketones Extraction Experiments 15/

8 viii CONTENTS Stability Constants Complexation Selectivities Ion Transport Calixarene Amides Calixarenes with Mixed Ligating Functional Groups Relation between Physicochemical Properties and Molecular Structure Conclusions and Perspectives 170 Acknowledgements 171 References 171 S. SHINKAI: Functionalized Calixarenes: New Applications as Catalysts, Ligands, and Host Molecules Introduction Syntheses of Functionalized Calixarenes Conformational Properties Acidity Constants of the Phenolic Hydroxyl Groups Aggregation and Inclusion Phenomena Chiral Calixarenes Ionophoric Calixarenes Conclusions 195 References 196 J. L. ATWOOD and S. G. BOIT: Water Soluble Calixarene Salts. A Class of Compounds with Solid-State Structures Resembling Those of Clays 1. Introduction 2. The [Calix[4]arene Sulfonatep- Anion 2.1. Nas[Calix[4]arene Sulfonate] 2.2. Other Alkali Salts 2.3. Transition Metals and Lanthanides 2.4. Inclusion of Organic Species 3. The [Nitrocalix[4]arene]2- Anion 4. The [Calix[4]arene Sulfonate Methyl Ether]4- Anion References J.-C. G. BDNZLI and J. MacB. HARROWFIELD: Lanthanide Ions and Calixarenes Introduction Lanthanide Ions and p-tert-butylcalixarenes Synthesis and Stoichiometry Complexes of p-tert-butylcalix[8]arene Complexes of p-tert-butylcalix[6]arene Complexes of p-tert-butylcalix[4]arene and p-tert-butylbishomooxacalix[4]arene Solid State Structures - X-Ray Crystallography 216

9 CONTENTS Complexes of p-tert-butylcalix[8jarene Complexes of p-tert-butylcalix[6jarene Complexes of p-tert-butylcalix[4jarene 2.3. Solution Structure 2.4. Luminescence Spectroscopy 3. Conclusions Acknowledgements References ix PART FOUR: INDUSTRIAL APPLICATIONS R. PERRIN and S. HARRIS: Industrial Applications of Calixarenes 1. Introduction 2. Recovery of Cesium 3. Recovery of Uranium 4. Further Ion Sequestering Possibilities 5. Ion Selective Electrodes and Field Effect Transistors 6. Phase Transfer Agents 7. Accelerators for Instant Adhesives 8. Ion Scavengers for Electronic Devices 9. Stabilizers for Organic Polymers 10. Separation of Neutral Organic Molecules 11. Hydrolysis Catalysts 12. Langmuir-Blodgett Films and Membranes 13. Polymer-Bound Calixarenes 14. Concluding Remarks References LIST OF CONTRIBUTORS

10 Preface The tenn "calixarenes", introduced in 1978 by D. Gutsche to describe the cyclic oligomers produced by condensation of p-substituted phenols with fonnaldehyde, is now universally accepted in the chemical community. The condensation of phenol with fonnaldehyde was studied in the last century by A. von Baeyer. Early in this century, L. Baekeland produced the first entirely synthetic polymers from phenol-fonnaldehyde condensates and the possibility that cyclic condensation products could be obtained from t-butylphenol, and fonnaldehyde was mentioned as early as in the beginning of the 1940's by A. Zinke. Despite their long history, the realisation that calixarenes may have very significant applications and uses in supramolecular chemistry is a relatively recent phenomenon. Calixarene chemistry, in contrast to their discovery, started slowly in the 1970's but rapidly gained momentum throughout the 1980's. Following C. Pedersens discovery of the crown ethers and the seminal developments of J.-M. Lehn and D. Cram with cryptands and spherands - all three honoured with the 1987 Nobel Chemistry Prize - the time was right for a surge of interest in research areas, frequently referred to as host-guest chemistry, receptor or supramolecular chemistry, and including important comparisons with biological processes and the development of new advanced materials. Now, the cyclic, bowl or basket-shaped calixarene molecules were looked on in a different light. Rather than "having developed from harmful by-products of phenoplasts manufacture" they were now seen as potentially valuable macrocyclic receptor molecules. Coincidentally, analytical techniques were available which enabled the calixarenes to be fully characterized some 30 years after their first synthesis. This book, which we have had the pleasure of editing, contains contributions from leading scientists in the field of calixarene chemistry. In ten chapters, it contains a timely comprehensive survey of the contemporary literature including much, unpublished data. Part one deals with the history and the synthesis of calixarenes, as well as with their chemical modification which has already led to numerous sophisticated host molecules. Part two describes the confonnation of calixarenes and their derivatives in the solid state. It demonstrates that X-ray analysis was one of the important tools for elucidating the structure of these compounds, as well as their inclusion properties. In part three the inclusion of various guests (ions and neutral molecules) in solution and in the solid state is treated in detail. The area spans from kinetically stable complexes to enzyme-like catalysis, from selective recognition at the air-water interface to confonnational or micellar properties in solution. Selective ionophores for sodium or potassium are described as well as uranophiles. Complexes with lanthanides are described as solid state structures similar to clays. Many of these properties are the basis for existing or potential industrial applications, a survey of which, including the patent literature, is presented in part four. We hope that this selection of topics will appeal to many readers, experts in the field of xi

11 xii PREFACE host-guest chemistry, as well as beginners. We also hope that part of the fascination exerted by calixarenes on us and the other authors of this book will also be felt by the readers, a fascination which prompted S. Shinkai to claim calixarenes to be another "supermolecule" in host-guest chemistry. September 1990 JACQUES VICENS VOLKER BOHMER