Tautomerism

Concepts and Applications in Science and Technology
1. Auflage 2016
ISBN: 978-3-527-33995-2
Verlag: WILEY-VCH

Buch, Englisch, 377 Seiten, Format (B × H): 178 mm x 252 mm, Gewicht: 921 g

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.

Autoren/Hrsg.

Antonov, Liudmil

Fachgebiete

• Naturwissenschaften Chemie Organische Chemie
• Naturwissenschaften Chemie Anorganische Chemie Festkörperchemie
• Naturwissenschaften Chemie Physikalische Chemie
• Naturwissenschaften Chemie Analytische Chemie

Inhaltsverzeichnis

List of Contributors XV

Preface XIX

1 Tautomerism: A Historical Perspective 1
José 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 ß-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 p-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
Frédéric Castet and Benoît 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, J

Über Autor(innen)

Liudmil Antonov is Professor of Physical Organic and Organic Analytical Chemistry at Bulgarian Academy of Sciences. Having obtained MSc (1989) and PhD (1994) degrees from the University of Sofia, he spent one year at Tokyo Institute of Technology before taking an appointment at University of Forestry (UF) in Sofia. In 1998, he was appointed as youngest in Bulgaria Associated Professor in Analytical Chemistry and from 1999 to 2002 headed the Department of Chemistry UF. After stays at AIST (Japan, 2002, 2006) as JSPS Fellow and at Humboldt University of Berlin (2003-2004) as Alexander von Humboldt Fellow and work for European Commission as reviewer and panel member (Directorate General for Research, 2001-2005), he joined Bulgarian Academy of Sciences in 2007. He has authored more than 90 research papers, reviews and book chapters, being cited over 1500 times.