Calixarenes An Introduction
This book gives a concise, comprehensive overview of the field with particular attention to the historical development of Calixarenes and will be of immediate value to researchers, graduates and professionals, Calixarenes belong to a family of macrocyclic compounds based on a hydrozyalkylation produ...
Main Author: | |
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Other Authors: | , , |
Format: | eBook |
Language: | English |
Published: |
Cambridge
Royal Society of Chemistry
2008
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Edition: | 2nd New ed |
Online Access: | |
Collection: | RSC eBook Collection 1968-2009 - Collection details see MPG.ReNa |
Table of Contents:
- 7.3: Solution State Complexes of Metal Cations with Exo Rim-substituted Calixarenes
- 7.4: Anion Complexes with Calixarenes
- 7.5: Salt Complexes with Calixarenes
- 7.6: Solution State Complexes of Molecules with Calixarenes
- 7.6.1: Complexes with Molecular Cations
- 7.6.2: Complexes with Neutral Molecules
- 7.6.2.1: Complexes in Aqueous Solution
- 7.6.2.2: Complexes in Non-aqueous Solution
- 7.7: Gas Phase Complexes
- 7.8: Theoretical Calculations
- 7.9: Templation
- 7.9.1: Templation in Calixarene Synthesis
- 7.9.2: Calixarenes as Templates
- 7.9.3: Templation in Conformational Phenomena
- 7.9.4: Allosteric Effects
- 7.10: Concluding Remarks
- Chapter 8: Using the Baskets: Calixarenes in Action
- 8.1: Calixarenes for Separation
- 8.1.1: Separation of Ions
- 8.1.2: Separation of Molecules
- 8.2: Calixarenes as Sensors
- 8.2.1: Ion- and Molecule-Selective Electrodes
- 8.2.2: Field Effect Transistors
- 8.2.3: Chromogenic and Fluorescent Sensors
- 8.2.4: Nonlinear Optical Compounds
- 8.2.5: Other Sensors
- 8.3: Calixarenes as Catalysts
- 8.3.1: Biomimetic Catalyst
- 8.3.2: Non-Biomimetic Catalysts
- 8.4: Calixarenes as Biomimetic and Physiological Compounds
- 8.5: Miscellaneous Applications
- 8.6: Patent Literature
- 8.7:Concluding Remarks
- Chapter 1: From Resinous Tar to Molecular Basket
- 1.1: The Resinous Tar
- 1,2: Glistening Crystals: The Zinke Products
- 1,3: More Crystals: The Niederl Products
- 1.4: Cyclic Tetramers: Proofs of Structure
- 1.5: The Petrolite Chapter
- 1.6: Cyclic Tetramers and the Quest for Enzyme Mimics
- 1.7: Unraveling the Literature
- 1.8: Nomenclature and Representation of the Calixarenes
- Chapter 2: Making the Baskets: Synthesis of Calixarenes
- 2.1: One-step, Base-Induced Syntheses of Phenol-derived Calixarenes
- 2.1.1: Synthesis of p-tert-Butylcalixarenes
- 2.1.2: Synthesis of Other p-Substituted Calixarenes
- 2.2: One-step, Acid-catalyzed Synthesis of Calixarenes
- 2.2.1: Phenol-derived Calixarenes
- 2.2.2: Resorcinol-derived Calixarenes
- 2.3: Multi-step Synthesis of Calixarenes
- 2.3.1: Non-convergent Stepwse syntheses
- 2.3.2: Convergent Stepwise Syntheses (Fragment Condensation Procedure)
- 2.4: Synthesis of Calixarene-related Compounds
- 4.2: Computationl studies of Calixarene Conformations
- 4.3: Conformations of Calixarenes in the Solid State
- 4.3.1: Calix[4]arenes
- 4.3.2: Calix[5]arenes
- 4.3.3: Calix[6]arenes
- 4.3.4: Calix[7]arenes
- 4.3.5: Calix[8]arenes
- 4.3.6: Large Calixarenes
- 4.4: Conformations of Flexible Calixarenes in Solution
- 4.4.1: Conformational Mobility of Calix[n]arenes
- 4.4.1.1: Conformations of Calix[4]arenes
- 4.4.1.2: Conformational Mobility of Calixarenes Lager than Calix[4]arenes
- 4.4.1.3: Conformational Mobility of Oxacalixarenes and Azacalixarenes
- 4.4.1.4: Conformational Mobility of Calixresorcarenes and C-Substituted Calixarenes
- 4.4.1.5: Conformational Mobility of Thiacalixarenes
- 4.4.1.6: Conformational Mobility of Calixarene Ethers, Deoxycalixarenes, Calixaquinones and Calixarenetiols
- 4.4.2: Pathways for Cone-cone Interconvesion of Calix[4]arenes
- 4.5: Conformationally Immobile Calixarenes
- 5.1.2.1: With Simple Alkyl Halides
- 5.1.2.2: With Functionalized Alkylating Agents
- 5.1.3: Endo Rim-bridged Calixarenes
- 5.1.4: Replacement of OH with H, N and S
- 5.2: Modifying the Exo Rim of Calixarenes
- 5.2.1: General Overview
- 5.2.2: Halogenation, Nitratin, Sulfonation and Diazonium Coupling Reactions
- 5.2.3: Alkylation (including Chloromethylation) Route
- 5.2.4: Acylation and Aroylation Routes
- 5.2.5: Arylation Reactions
- 5.2.6: Aminomethyation: The p-Quinonemethide Route
- 5.2.7: p-Claisen Rearrangement Route
- 5.3: Functionalization of the Methylene Bridges
- 5.4: Exo Rim-Bridged Calixarenes
- 5.5: Oxidation of Calixarenes
- 5.5.1: Calixquinones
- 5.5.2: Spirodienones
- 5.6: Reduction of Calixarenes
- 5.7: Selective Functionalizaton
- 5.8: Concluding Remarks
- Chapter 6 : Combining the Baskets: Multi-Calixarenes
- 6.1: Calixarenes Intermolecularly Bridged by Covalent Bonding
- 6.1.1: Bridging the Endo Rims, 6.1.2: Bridging the Exo Rims
- 2.4.1: Norcalixarenes and Homocalixarenes
- 2.4.2: Oxacalixarenes, Azacalixarenes, and Thiacalixarenes
- 2.4.3: Homooxacalixarenes and Homoazacalixarenes
- 2.4.4: Heterocalixarenes
- 2.5: Mechanism of Calixarene-forming Reactions
- 2.5.1: Mechanism of the Base-induced Reactioin
- 2.5.2: Mechanism of the Acid-catalyzed Reaction
- 2.6: Concluding Remarks
- Chapter 3 Proving the Baskets: The Characterization and Properties of Calixarenes
- 3.1: Separation and Purfiication of Calixarenes
- 3.2: X-Ray Crystallography: The Ultimate Proof of Structure 3.3: Physical Properties of Calixarenes
- 3.3.1 : Melting Points
- 3.3.2: Solubilities
- 3.3.3: pKa Values
- 3.4: Dipole Moments of Calixarenes
- 3.5: Spectral Properties of Calixarenes
- 3.5.1: Infrared Spectra
- 3.5.2: Ultraviolet Spectra
- 3.5.3: NMR Spectra
- 3.5.4: Mass Spectra
- 3.6: Concluding Remarks
- Chapter 4: Shaping the Baskets: Conformations of Calixarenes
- 4.1: Conformational Representation and Nomenclature
- 6.1.3: Multi-Calxarenes and Calixarene Dendrimers
- 6.2: Calixarenes Intermolecular Bridged by Non-covalent Bonding
- 6.2.1: Dimeric Assemblies of Calixarenes
- 6.2.2: Catenanes and Rotaxanes
- 6.2.3: Oligomeric and Polymeric Assemblies of Calixarenes
- 6.2.4: Calixarenes in Monolayers and Interfaces
- 6.3: Calixarene Polymers
- 6.4: Concluding Remarks
- Chapter 7: Filling the Baskets: Complex Formation with Calixarenes
- 7.1: Solid State Complexes
- 7.2: Solution State Complexes of Metal Cations with Endo Rim-substituted Calixarenes
- 7.2.1: Complexation with Parent Calixarenes
- 7.2.2: Complexation with Endo Rim-substituted Calixarenes
- 7.2.1.1: Endo Rim Ethers
- 7.2.1.2: Endo Rim Esters
- 7.2.1.3: Endo Rim Ketones
- 7.2.1.4 Endo Rim Amides
- 7.2.1.5: Endo Rim Carboxylic Acids
- 7.2.1.6: Endo Rim Phosphorus- and Sulfur-containing Groups
- 7.2.1.7: Nitrogen-containing Chelating Groups on Endo Rim
- 7.2.3: Calixcrowns
- 7.2.4: Calixspherands
- 4.5.1: Minimum Structural Requirements for Conformational Immobility of Unbridged Calixarene Ethers and Esters
- 4.5.1.1: Identification of Fixed Conformers
- 4.5.1.2: Fully Etherified and Esterified Calixarenes
- 4.5.1.3: Partially Etherified and Esterified Calixarenes
- 4.5 1.4: Meta-substituted Calixarenes
- 4.5.2: Conformational Immobilization via Bridging
- 4.5.3: Conformational Freezing via Oxygen-Metal Bridges
- 4.6: Factors Governing the Conformational Outcome of Derivitazation
- 4.6.1: O-Tetrasubstitution of Calix[4]arenes
- 4.6.2: Mono-, Di- and Tri-O-substitution of Calix[4]arenes
- 4.6.3: O-Substitution of Calix[5]arenes and Calix[6]arenes
- 4.6.4: Calixarene Oxyanions
- 4.6.4.1: Calix[4]arene Oxyanions
- 4.6.4.2: Calix[6]arene Oxyanions
- 4.7: Chiral Calixarenes
- 4.8: Concluding Remarks
- Chapter 5: Embroidering the Baskets: Introduction of Functional Groups
- 5.1: Functionalization Involving the OH Groups
- 5.1.1: Esterfication
- 5.1.2: Etherification