Calixarenes: A Versatile Class of Macrocyclic Compounds

ISBN-13: 9789401074025 / Angielski / Miękka / 2011 / 264 str.

Jacques Vicens; Volker Bohmer

Opis

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.

Recenzje

'This book that deals with a special class of host-guest chemistry, recognized by the 1987 Nobel Chemistry Prize Awards, should appeal to almost all chemists. Medicinal chemists, in particular, may find it a source of novel new approaches to potential therapeutic agents.' Journal of Medicinal Chemistry 35:7 1992

Spis treści

One: History and Synthesis of Calixarenes.- Single Step Synthesis and Properties of Calixarenes.- 1. Introduction.- 2. Single Step Synthesis of Calixarenes.- 2.1. Base-Induced Procedures.- 2.2. Acid-Catalyzed Procedures.- 2.3. Thermally Induced Procedures.- 3. Synthesis of Functionalized Calixarenes.- 3.1. Introduction of Substituents on the ‘Lower Rim’ of Phenol-Derived Calixarenes.- 3.1.1. Ester and Ether Formation with Monofunctionalized Reagents.- 3.1.2. Esterification and Etherification with Polyfunctionalized Reagents.- 3.2. Introduction of Substituents on the ‘Upper Rim’ of Phenol-Derived Calixarenes.- 3.2.1. Dealkylation of p-Alkylcalixarenes.- 3.2.2. Electrophilic Substitution Route.- 3.2.3. p-Claisen Rearrangement Route.- 3.2.4. p-Quinonemethide Route.- 3.2.5. p-Chloromethylation Route.- 3.3. Introduction of Substituents at the ‘Upper Rim’ of Resorcinol-Derived Calixarenes.- 3.4. Introduction of Functional Groups at the Methylene Bridges of Calixarenes.- 4. Physical Properties of Calixarenes.- 4.1. Melting Points.- 4.2. Solubilities.- 4.3. Spectral Properties of Calixarenes.- 4.3.1. Infrared Spectra.- 4.3.2. Ultraviolet Spectra.- 4.3.3. NMR Spectra.- 4.3.4. Mass Spectra.- 5. Concluding Comments.- References.- Special Calixarenes, Synthesis and Properties.- 1. Introduction.- 2. Stepwise Synthesis of Calixarenes.- 3. Fragment Condensation.- 4. Selective Functionalization.- 5. The First Acidity Constant of Calix[4]arenes.- 6. Chiral Calix[4]arenes.- 7. Bridged Calixarenes.- 8. Double Calixarenes and Future Directions.- References.- Two: X-Ray Structural Data on Calixarene Architectures.- Conformations of Calixarenes in the Crystalline State.- 1. Introduction.- 2. Conformations and Structures of Some Precursors.- 3. Conformations of Calixarenes.- 3.1. Introduction.- 3.2. Conformations of Calix[4]arenes.- 3.2.1. Calix[4]arenes with a Fourfold Axis.- 3.2.3. Calix[4]arenes with Symmetry Planes.- 3.2.3. Calix[4]arenes with a Twofold Axis.- 3.2.4. Calix[4]arenes in the Cone Conformation with No Particular Symmetry.- 3.3. Conformations of Calix[5]arenes.- 3.4. Conformations of Calix[6]arenes.- 3.4.1. Calix[6]arenes with Symmetry Planes.- 3.4.2. Calix[6]arenes in the Centrosymmetrical Conformation.- 3.5. Conformations of Calix[7]arenes.- 3.6. Conformations of Calix[8]arenes.- 3.6.1. Calix[8]arenes with Mirror Planes.- 4. Conclusion.- References.- Inclusion Properties and Host—Guest Interactions of Calixarenes in the Solid State.- 1. Introduction.- 1.1. General Considerations.- 1.2. Conformational Properties of Calixarenes in the Solid State.- 2. Conformational Preferences in Functionalized Calixarenes.- 2.1. Calix[4]arenes.- 2.2. Calix[6]arenes.- 2.3. Calix[8]arenes.- 2.4. Calixarene Cavitands.- 3. Metallocalixarenes.- 4. Calixarene Based Cation Carriers and Receptors.- 5. Molecular Inclusion of Neutral Molecules by Calixarenes.- 5.1. Intramolecular Complexes of Calixarenes.- 5.2. Cage Complexes.- 5.3. Intermolecular Complexes.- 5.4. Clathrates.- 6. Theoretical Models for the Host—Guest Interactions.- Acknowledgements.- References.- Three: Inclusion Properties of Calixarenes and Their Derivatives.- Calixarene-Based Cation Receptors and Carriers.- 1. Introduction.- 2. Calixarene Podands with Ether Chains.- 3. Calixarene Podands with Ester and Amide Groups.- 4. Calixcrowns and Calixspherands.- 5. Ionizable Calixarene Ligands.- 6. Concluding Remarks.- Acknowledgements.- References.- Chemically Modified Calixarenes as New Selective Receptors for Monovalent Cations.- 1. Introduction.- 2. Calixarenes as Receptor Substructures.- 3. Chemically Modified Calixarenes.- 4. Complexation of Alkali Cations: Phase Transfer, Stability Constants, Selectivities, and Transport.- 4.1. Calixarene Esters and Ketones.- 4.1.1. Extraction Experiments.- 4.1.2. Stability Constants.- 4.1.3. Complexation Selectivities.- 4.1.4. Ion Transport.- 4.2. Calixarene Amides.- 4.3. Calixarenes with Mixed Ligating Functional Groups.- 4.4. Relation between Physicochemical Properties and Molecular Structure.- 5. Conclusions and Perspectives.- Acknowledgements.- References.- Functionalized Calixarenes: New Applications as Catalysts, Ligands, and Host Molecules.- 1. Introduction.- 2. Syntheses of Functionalized Calixarenes.- 3. Conformational Properties.- 4. Acidity Constants of the Phenolic Hydroxyl Groups.- 5. Aggregation and Inclusion Phenomena.- 6. Chiral Calixarenes.- 7. Ionophoric Calixarenes.- 8. Conclusions.- References.- Water Soluble Calixarene Salts. A Class of Compounds with Solid-State Structures Resembling Those of Clays.- 1. Introduction.- 2. The [Calix[4]arene Sulfonate]5- Anion.- 2.1. Na5[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.- Lanthanide Ions and Calixarenes.- 1. Introduction.- 2. Lanthanide Ions and p-fert-Butylcalixarenes.- 2.1. Synthesis and Stoichiometry.- 2.1.1. Complexes of p-tert-Butylcalix[8]arene.- 2.1.2. Complexes of p-tert-Butylcalix[6]arene.- 2.1.3. Complexes of p-tert-Butylcalix[4]arene and p-tert-Butylbishomooxacalix[4]arene.- 2.2. Solid State Structures — X-Ray Crystallography.- 2.2.1. Complexes of p-tert-Butylcalix[8]arene.- 2.2.2. Complexes of p-tert-Butylcalix[6]arene.- 2.2.3. Complexes of p-tert-Butylcalix[4]arene.- 2.3. Solution Structure.- 2.4. Luminescence Spectroscopy.- 3. Conclusions.- Acknowledgements.- References.- Four: Industrial Applications.- 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.