| Preface |
| General Remarks |
| Abbreviations |
| Chapter 1 Introduction 1 |
| 1.1 Effect of Fluorine on Physical Properties 1 |
| 1.1.1 Mimic and Block Effects 1 |
| 1.1.2 Effect of the Electron-withdrawing Nature of Fluorine 3 |
| 1.1.2.1 Deactivation Effect 3 |
| 1.1.2.2 Activation Effect 5 |
| 1.1.3 Conformational Preference Including Hydrogen Bonding Ability 7 |
| 1.1.4 Steric Size of Fluorine-containing Groups 9 |
| 1.2 Effect of Fluorine on Chemical Reactivity 10 |
| 1.2.1 Stability of Cationic or Anionic Species Next to Fluorine or Fluoroalkyl Groups 10 |
| 1.2.2 SN1 and SN2 Reactivity of Fluorinated Materials 14 |
| 1.3 Preparation of Fluorine-containing Materials 16 |
| 1.4 Handling Fluorinated Materials 20 |
| 1.5 References and Notes 21 |
| Chapter 2 Preparation of Monofluorinated Materials 31 |
| 2.1 Fluorination 31 |
| 2.1.1 Nucleophilic Fluorination (Substitution) 31 |
| 2.1.2 Nucleophilic Fluorination (Addition) 42 |
| 2.1.3 Nucleophilic Fluorination (Miscellaneous) 44 |
| 2.1.4 Electrophilic Fluorination 45 |
| 2.2 Carbon-Carbon Bond-forming Reactions 49 |
| 2.2.1 Aldol Type Reactions 49 |
| 2.2.2 Wittig Type Reactions 53 |
| 2.2.3 Rearrangement and Cycloaddition 57 |
| 2.2.4 Alkylations 59 |
| 2.2.5 Miscellaneous 62 |
| 2.3 Removal of Fluorine from Difluorinated Materials 68 |
| 2.4 Optically Active Materials by Bioorganic Methods 70 |
| 2.5 Substitution Reactions 72 |
| 2.6 Miscellaneous Reactions 74 |
| Chapter 3 Preparation of Difluorinated Materials 79 |
| 3.1 Fluorination 79 |
| 3.1.1 Nucleophilic Fluorination 79 |
| 3.1.2 Electrophilic Fluorination 81 |
| 3.1.3 Miscellaneous 82 |
| 3.2 Difluoromethylenation 83 |
| 3.3 Introduction of Difluoromethyl and Related Groups 85 |
| 3.4 Carbon-Carbon Bond-forming Reactions 91 |
| 3.4.1 Reformatsky Type Reactions 91 |
| 3.4.2 Aldol Reactions and Claisen Condensation 95 |
| 3.4.3 Diels-Alder Reactions 98 |
| 3.4.4 Claisen Rearrangement 100 |
| 3.4.5 Alkylations and Acylations 102 |
| 3.5 Removal of Fluorine from Trifluorinated Materials 106 |
| 3.6 Reactions of Hemiacetals 111 |
| 3.7 Oxidations and Reductions 115 |
| 3.8 Miscellaneous Reactions 118 |
| Chapter 4 Preparation of Trifluorinated Materials 121 |
| 4.1 Introduction of a Trifluoromethyl Group 121 |
| 4.1.1 Introduction of a Trifluoromethyl Group (Nucleophilic) 121 |
| 4.1.2 Introduction of a Trifluoromethyl Group (Electrophilic, Radical) 127 |
| 4.1.3 Introduction of a Trifluoromethyl Group (Miscellaneous) 131 |
| 4.2 Conversion to a Trifluoromethyl Group 132 |
| 4.3 Carbon-Carbon Bond-forming Reactions 135 |
| 4.3.1 Aldol Type Reactions 135 |
| 4.3.2 Michael Reactions 140 |
| 4.3.3 Ene Reactions 146 |
| 4.3.4 Diels-Alder Reactions and 1,3-Dipolar Cycloadditions 148 |
| 4.3.5 Wittig Type Reactions 152 |
| 4.3.6 Rearrangements 154 |
| 4.3.7 Nucleophilic Additions 158 |
| 4.3.8 Electrophilic Additions 166 |
| 4.3.9 Miscellaneous 172 |
| 4.4 Reactions with Hetero Nucleophiles 175 |
| 4.4.1 Reactions with Nitrogen Nucleophiles 175 |
| 4.4.2 Reactions with Oxygen Nucleophiles 177 |
| 4.4.3 Reaction with a Sulfur Nucleophile 181 |
| 4.5 Dehydrations 183 |
| 4.6 Oxidations and Reductions 184 |
| 4.6.1 Oxidations 184 |
| 4.6.2 Reductions 189 |
| 4.7 Optical Resolutions 194 |
| 4.7.1 Bioorganic Methods 194 |
| 4.7.2 Chemical Method 198 |
| 4.8 Miscellaneous Reactions 199 |
| Chapter 5 Preparation of Poly- or Perfluorinated Materials 209 |
| 5.1 Introduction of Poly- or Perfluorinated Groups 209 |
| 5.1.1 Introduction of Poly- or Perfluorinated Groups (Nucleophilic) 209 |
| 5.1.2 Introduction of Poly- or Perfluorinated Groups (Electrophilic, Radical) 212 |
| 5.2 Carbon-Carbon Bond-forming Reactions 216 |
| 5.2.1 Aldol Type Reactions 216 |
| 5.2.2 Wittig Reactions 221 |
| 5.2.3 Alkylations 223 |
| 5.2.4 Anti-Michael Reactions 225 |
| 5.2.5 Miscellaneous 228 |
| 5.3 Miscellaneous Reactions 230 |
| Appendix Representative Distributors of Fluorochemicals 233 |
| Appendix Availability of Fluorinated Reagents 235 |
| Compound Index 239 |
| Reagent Index 243 |
| Product Index 247 |
| Author Index 256 |
図書
図書
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