Tautomerism : concepts and applications in science and technology
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Tautomerism : concepts and applications in science and technology
Wiley-VCH, c2016
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注記
Includes bibliographical references and index
内容説明・目次
内容説明
Reflecting the substantially increased interest in tautomerism, this book demonstrates the transformation of fundamental knowledge into novel concepts and the latest applications. Each chapter introduces the theoretical background, before reviewing and critically discussing the experimental techniques and corresponding applications. Special emphasis is placed on tautomerism under unusual conditions, such as in supramolecular solids and at surfaces, displaying the wide scope between basic research and timely applications.
目次
List of Contributors XV
Preface XIX
1 Tautomerism: A Historical Perspective 1
Jose Elguero
1.1 Thermodynamic Aspects 2
1.2 Kinetic Aspects 5
1.3 Conclusions 6
References 7
2 "Triage" for Tautomers: The Choice between Experiment and Computation 11
Peter J. Taylor and Liudmil Antonov
2.1 Introduction (Original TextWritten by Peter J. Taylor) 11
2.2 cis-Amides 12
2.3 Tautomerism in Alicyclic Lactams: Six-Membered Rings 13
2.4 Tautomerism in Alicyclic Lactams: 2-Pyrrolidinone 14
2.5 Tautomerism in Other Five-Membered Ring Lactams 16
2.6 Tautomeric Ratios Requiring Computation: Alicyclic -Diketones 17
2.7 Tautomeric Ratios Requiring Computation: "Maleic Hydrazide" 18
2.8 Tautomer Ratios Requiring Computation: 2-Oxo Derivatives of Pyrrole, Furan, andThiazole 20
2.9 Tautomeric Ratios Requiring Computation: Compounds Containing Contiguous Carbonyl Groups 22
2.10 Tautomeric Ratios Requiring Computation: Compounds Containing Contiguous -Donors 24
2.11 Compounds Equally Suited to Experiment or Computation: "Azapentalenes" 25
2.12 Phenomena Susceptible to Experiment or Computation: Lone Pair Effects 29
2.13 Conformational Effects on Aminoenone Stability: A Computational Approach 30
2.14 Overview (Original TextWritten by Peter J. Taylor) 32
References 32
3 Methods to Distinguish Tautomeric Cases fromStatic Ones 35
Poul Erik Hansen
3.1 Introduction 35
3.2 The Liquid State 36
3.3 UV/VIS Spectroscopy 53
3.4 Infra Red Spectroscopy 55
3.5 Tautomerism in the Excited State 56
3.6 Near-Edge X-Ray 56
3.7 Energy-Dispersive X-Ray 57
3.8 Solid State 57
3.9 Single Molecule Tautomerization 59
3.10 Gas Phase 60
3.11 Theoretical Calculations 61
References 71
4 Electron-Transfer-Induced Tautomerizations 75
Thomas Bally
4.1 Introduction 75
4.2 Methodology 76
4.3 O-Alkyl Phenyl Ketones 77
4.4 Conclusions 93
Acknowledgments 93
References 94
5 The Fault Line in Prototropic Tautomerism 95
Peter J. Taylor and Liudmil Antonov
5.1 Introduction: "N-Type" and "C-Type" Tautomerism 95
5.2 Tautomerism in Symmetrical Amidines 96
5.3 Tautomer Ratio in Asymmetric Heteroaromatic Amidines 100
5.4 Tautomer Ratio in the Imine-Enamine System: Substitution at Nitrogen 102
5.5 Tautomer Ratio in the Imine-Enamine System: Substitution at Carbon 105
5.6 The Resonance Contribution to Ketone and Amide Tautomerism 107
5.7 The Field-Resonance Balance in Vinylogous Heteroaromatic Amidines 108
5.8 Conclusions 110
References 111
6 Theoretical Consideration of In-Solution Tautomeric Equilibria in Relation to Drug Design 113
Peter I. Nagy
6.1 Introduction 113
6.2 Methodology 114
6.3 Equilibration Mechanism 119
6.4 Relation to Drug Design 123
6.5 In-solution Equilibrium Calculations 127
6.6 Concluding Remarks 142
References 143
7 Direct Observation and Control of Single-Molecule Tautomerization by Low-Temperature Scanning Tunneling Microscopy 147
Takashi Kumagai and Leonhard Grill
7.1 Brief Introduction to STM 148
7.2 Direct Observation of Single-Molecule Tautomerization Using STM 152
7.3 Concluding Remarks 172
Acknowledgments 172
References 172
8 Switching of the Nonlinear Optical Responses of Anil Derivatives: From Dilute Solutions to the Solid State 175
Frederic Castet and Benoit Champagne
8.1 Introduction 175
8.2 Experimental and Theoretical Methods 178
8.3 Second-Order Nonlinear Optical Responses of Anils 187
8.4 Conclusions 196
Acknowledgments 197
References 197
9 Tautomerism in Oxoporphyrinogens and Pyrazinacenes 203
Jonathan P. Hill, Jan Labuta, Shinsuke Ishihara, Gary J. Richards, Yongshu Xie, Francis D'Souza, and Katsuhiko Ariga
9.1 Introduction 203
9.2 Tautomerism in Oxoporphyrinogen, OxP 205
9.3 Multichromic Acidity Indicator Involving Tautomerism 211
9.4 Polytautomerism in Oxocorrologen, OxC 212
9.5 Tautomerism in Linear Reduced Fused Oligo-1,4-pyrazines (Pyrazinacenes) 219
9.6 Conclusion 225
References 226
10 Enolimine-Ketoenamine Tautomerism for Chemosensing 229
Alexander D. Dubonosov, Vladimir A. Bren, and Vladimir I.Minkin
10.1 Introduction 229
10.2 Prototropic Enolimine-Ketoenamine Tautomerism 229
10.3 Ionochromic Enolimine-Ketoenamine Tautomeric Systems for Ions Sensing 234
10.4 Concluding Remarks 247
Acknowledgments 247
References 247
11 Tautomerizable Azophenol Dyes: Cornerstones for Advanced Light-Responsive Materials 253
Jaume Garcia-Amoros and Dolores Velasco
11.1 Azobenzene-Based Light-Sensitive Materials 253
11.2 Azophenols: Tautomerizable Photochromes with Fast Switching Speeds 255
11.3 Sub-Millisecond Thermally Isomerizing Azophenols for Optically Triggered Oscillating Materials 262
11.4 Fast-Responding Artificial Muscles with Azophenol-Based Liquid Single Crystal Elastomers 266
11.5 Conclusion 268
References 269
12 Controlled Tautomerism: Is It Possible? 273
Daniela Nedeltcheva-Antonova and Liudmil Antonov
12.1 Introduction 273
12.2 Manipulation of Electronic Properties of the Substituents 275
12.3 Tautomeric Tweezers 278
12.4 Tautomeric Cavities 279
12.5 Proton Cranes 282
12.6 Rotary Switches 290
12.7 Concluding Remarks 291
Acknowledgments 291
References 291
13 Supramolecular Control over Tautomerism in Organic Solids 295
Krunoslav U arevic, Vladimir Stilinovic, and Mirta Rubcic
13.1 Crystal Engineering and Tautomerism in Molecular Solids 297
13.2 Supramolecular Synthons 298
13.3 Solid-State Tautomerism, Proton Transfer, and Hydrogen Bonding 300
13.4 Supramolecular Stabilization of Metastable Tautomers 304
13.5 Identification of Tautomeric Properties and Connectivity Preferences 305
13.6 Synthetic Methods 306
13.7 Supramolecular Interactions in Other Tautomeric Solids 310
References 324
14 Proton Tautomerism in Systems of Increasing Complexity: Examples from Organic Molecules to Enzymes 329
Hans-Heinrich Limbach, Gleb S. Denisov, Ilya G. Shenderovich, and Peter M. Tolstoy
14.1 Introduction 329
14.2 Hydrogen Bond Geometries and Proton Transfer 330
14.3 Tautomerizations without Requiring Reorganization of the Environment 333
14.4 Tautomerizations Requiring Reorganization of the Environment 346
14.5 Conclusions 364
Acknowledgments 365
References 365
Index 373
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