Guide to fluorine NMR for organic chemists

著者

書誌事項

Guide to fluorine NMR for organic chemists

William R. Dolbier, Jr

Wiley, c2016

2nd ed

  • : cloth

大学図書館所蔵 件 / 全11件

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注記

Includes bibliographical references and index

内容説明・目次

内容説明

Following its well-received predecessor, this book offers an essential guide to chemists for understanding fluorine in spectroscopy. With over 1000 compounds and 100 spectra, the second edition adds new data - featuring fluorine effects on nitrogen NMR, chemical shifts, and coupling constants. * Explains how to successfully incorporate fluorine into target molecules and utilize fluorine substituents to structurally characterize organic compounds * Includes new data on nitrogen NMR, focusing on N-15, to portray the influence of fluorine upon nitrogen NMR chemical shifts and coupling constants * Expands on each chapter from the first edition with additional data and updated discussion from recent findings * "The flawless ordering of material covered in this stand-alone volume is such that information can be found very easily." - Angewandte Chemie review of the first edition, 2010

目次

PREFACE xv 1 GENERAL INTRODUCTION 1 1.1. Why Fluorinated Compounds are Interesting? / 1 1.1.1. Steric Size / 1 1.1.2. Polar Effects / 2 1.1.3. Effect of Fluorine Substituents on Acidity and Basicity of Compounds / 2 1.1.4. Effect of Fluorinated Substituents on Lipophilicity of Molecules / 3 1.1.5. Other Effects / 4 1.1.6. Analytical Applications in Biomedicinal Chemistry / 4 1.2. Introduction to Fluorine NMR / 5 1.2.1. Chemical Shifts / 5 1.2.2. Coupling Constants / 7 2 AN OVERVIEW OF FLUORINE NMR 9 2.1. Introduction / 9 2.2. Fluorine Chemical Shifts / 10 2.2.1. Some Aspects of Shielding/Deshielding Effects on Fluorine Chemical Shifts / 11 2.2.2. Solvent Effects on Fluorine Chemical Shifts / 15 2.2.3. Overall Summary of Fluorine Chemical Shift Ranges / 16 2.3. The Effect of Fluorine Substituents on Proton Chemical Shifts / 17 2.4. The Effect of Fluorine Substituents on Carbon Chemical Shifts / 18 2.5. The Effect of Fluorine Substituents on 31P Chemical Shifts / 19 2.6. The Effect of Fluorine Substituents on 15N Chemical Shifts / 20 2.7. Spin-Spin Coupling Constants to Fluorine / 23 2.7.1. Effect of Molecule Chirality on Coupling / 27 2.7.2. Through-Space Coupling / 29 2.7.3. Fluorine-Fluorine Coupling / 32 2.7.4. Coupling Between Fluorine and Hydrogen / 33 2.7.5. Coupling Between Fluorine and Carbon / 35 2.7.6. Coupling Between Fluorine and Phosphorous / 38 2.7.7. Coupling Between Fluorine and Nitrogen / 39 2.8. Second-Order Spectra / 40 2.9. Isotope Effects on Chemical Shifts / 45 2.10. Advanced Topics / 48 2.10.1. Multidimensional 19F NMR / 50 3 THE SINGLE FLUORINE SUBSTITUENT 55 3.1. Introduction / 55 3.1.1. Chemical Shifts - General Considerations / 56 3.1.2. Spin-Spin Coupling Constants - General Considerations / 56 3.2. Saturated Hydrocarbons / 57 3.2.1. Primary Alkyl Fluorides / 57 3.2.2. Secondary Alkyl Fluorides / 61 3.2.3. Tertiary Alkyl Fluorides / 63 3.2.4. Cyclic and Bicyclic Alkyl Fluorides / 66 3.3. Influence of Substituents/Functional Groups / 70 3.3.1. Halogen Substitution / 70 3.3.2. Alcohol, Ether, Epoxide, Ester, Sulfide, Sulfone, Sulfonate, and Sulfonic Acid Groups / 77 3.3.3. Amino, Ammonium, Azide, and Nitro Groups / 80 3.3.4. Phosphorous Compounds / 83 3.3.5. Silanes, Stannanes, and Germanes / 83 3.4. Carbonyl Functional Groups / 84 3.4.1. Aldehydes and Ketones / 85 3.4.2. Carboxylic Acid Derivatives / 86 3.4.3. 1H and 13C NMR Data for Aldehydes, Ketones, and Esters / 86 3.4.4. -Ketoesters, Diesters, and Nitroesters / 89 3.5. Nitriles / 89 3.5.1. 1H and 13C NMR Data for Nitriles / 89 3.6. Alkenes with a Single Fluorine Substituent / 90 3.6.1. Hydrocarbon Alkenes / 90 3.6.2. Conjugated Alkenyl Systems / 93 3.6.3. Allylic Alcohols, Ethers, and Halides / 94 3.6.4. Halofluoroalkenes and Fluorovinyl Ethers / 97 3.6.5. Geminal Fluoro, Hetero Alkenes / 98 3.6.6. Multifluoroalkenes / 98 3.6.7. , -Unsaturated Carbonyl Compounds / 101 3.7. Acetylenic Fluorine / 104 3.8. Allylic and Propargylic Fluorides / 105 3.8.1. 1H and 13C NMR Data / 106 3.9. Fluoroaromatics / 106 3.9.1. Monofluoroaromatics / 106 3.9.2. Fluoropolycyclic Aromatics: Fluoronaphthalenes / 111 3.9.3. Polyfluoroaromatics / 112 3.10. Fluoromethyl Aromatics / 114 3.11. Fluoroheterocycles / 119 3.11.1. Fluoropyridines, Quinolines, and Isoquinolines / 119 3.11.2. Fluoropyrimidines and Other Fluorine-Substituted Six-Membered Ring Heterocycles / 122 3.11.3. Fluoromethyl Pyridines and Quinolines / 123 3.11.4. Fluoropyrroles and Indoles / 123 3.11.5. Fluoromethyl Pyrroles and Indoles / 125 3.11.6. Fluorofurans and Benzofurans / 125 3.11.7. Fluoromethyl Furans and Benzofurans / 126 3.11.8. Fluorothiophene and Benzothiophene / 127 3.11.9. Fluoromethyl Thiophenes and Benzothiophenes / 128 3.11.10. Fluoroimidazoles and Pyrazoles / 128 3.11.11. Fluoromethyl and Fluoroalkyl Imidazoles, 1H-pyrazoles, Benzimidazoles, 1H-triazoles, Benzotriazoles, and Sydnones / 128 3.12. Other Common Groups with a Single Fluorine Substituent / 129 3.12.1. Acyl Fluorides / 130 3.12.2. Fluoroformates / 131 3.12.3. Sulfinyl and Sulfonyl Fluorides / 131 4 THE CF2 GROUP 133 4.1. Introduction / 133 4.1.1. Chemical Shifts - General Considerations / 134 4.1.2. Spin-Spin coupling Constants - General Considerations / 135 4.2. Saturated Hydrocarbons Containing a CF2 Group / 135 4.2.1. Alkanes Bearing a Primary CF2H Group / 136 4.2.2. Secondary CF2 Groups / 139 4.2.3. Discussion of Coupling Constants Within CF2 Groups / 142 4.2.4. Pertinent 1H Chemical Shift Data / 143 4.2.5. Pertinent 13C NMR Data / 146 4.3. Influence of Substituents/Functional Groups / 148 4.3.1. Halogen Substitution / 148 4.3.2. Alcohol, Ether, Esters, Thioether, and Related Substituents / 152 4.3.3. Epoxides / 155 4.3.4. Sulfoxides, Sulfones, Sulfoximines, and Sulfonic Acids / 156 4.3.5. Multifunctional , -Difluoro Alcohols / 157 4.3.6. Compounds with Two Different Heteroatom Groups Attached to CF2 Including Chloro- and Bromodifluoromethyl Ethers / 157 4.3.7. Amines, Azides, and Nitro Compounds / 158 4.3.8. Phosphines, Phosphonates, and Phosphonium Compounds / 162 4.3.9. Silanes, Stannanes, and Germanes / 162 4.3.10. Organometallics / 162 4.4. Carbonyl Functional Groups / 164 4.4.1. Aldehydes and Ketones / 164 4.4.2. Carboxylic Acids and Derivatives / 166 4.5. Nitriles / 168 4.5.1. 1H and 13C NMR Spectra of Nitriles / 168 4.6. Amino-, Hydroxyl-, and Keto-Difluorocarboxylic Acid Derivatives / 169 4.7. Sulfonic Acid Derivatives / 170 4.8. Alkenes and Alkynes / 170 4.8.1. Simple Alkenes with Terminal Vinylic CF2 Groups / 170 4.8.2. Conjugated Alkenes with Terminal Vinylic CF2 Group / 172 4.8.3. Cumulated Alkenes with a Terminal CF2 Group / 174 4.8.4. Effect of Vicinal Halogen or Ether Function / 174 4.8.5. Effect of Allylic Substituents / 174 4.8.6. Polyfluoroethylenes / 175 4.8.7. Trifluorovinyl Group / 175 4.8.8. , -Unsaturated Carbonyl Systems with a Terminal Vinylic CF2 Group / 176 4.8.9. Allylic and Propargylic CF2 Groups / 177 4.9. Benzenoid Aromatics Bearing a CF2H or CF2R Group / 178 4.9.1. 1H and 13C NMR Data / 179 4.9.2. CF2 Groups with More Distant Aryl Substitutents / 180 4.10. Heteroaromatic CF2 Groups / 180 4.10.1. Pyridines, Quinolones, Phenanthridines, and Acridines / 181 4.10.2. Furans, Benzofurans, Thiophenes, Pyrroles, and Indoles / 181 4.10.3. Pyrimidines / 183 4.10.4. Five-Membered Ring Heterocycles with Two Hetero Atoms: Imidazoles, Benzimidazoles, 1H-pyrazoles, Oxazoles, Isoxazoles, Thiazoles, and Indazoles / 183 4.10.5. Five-Membered Ring Heterocycles with Three or More Heteroatoms: Sydnones, Triazoles, and Benzotriazoles / 183 4.10.6. Various Other Difluoromethyl-Substituted Heterocyclic Systems / 185 5 THE TRIFLUOROMETHYL GROUP 187 5.1. Introduction / 187 5.1.1. NMR Spectra of Compounds Containing the CF3 Group - General Considerations / 187 5.2. Saturated Hydrocarbons Bearing a CF3 Group / 189 5.2.1. Alkanes Bearing a CF3 Group / 189 5.2.2. Cycloalkanes Bearing a CF3 Group / 189 5.2.3. 1H and 13C NMR Data, General Information / 191 5.3. Influence of Substituents and Functional Groups / 193 5.3.1. Impact of Halogens / 193 5.3.2. Ethers, Alcohols, Esters, Sulfides, and Selenides / 195 5.3.3. Sulfones, Sulfoxides, and Sulfoximines / 200 5.3.4. Amines and Nitro Compounds / 200 5.3.5. Trifluoromethyl Imines, Oximes, Hydrazones, Imidoyl Chlorides, Nitrones, Diazo and Diazirine Compounds / 204 5.3.6. Phosphines and Phosphonium Compounds / 205 5.3.7. Organometallics / 205 5.4. Boronic Esters / 207 5.5. Carbonyl Compounds / 207 5.5.1. 1H and 13C NMR Data / 209 5.6. Nitriles / 213 5.6.1. 13C NMR Data for Nitriles / 213 5.7. Bifunctional Compounds / 214 5.8. Sulfonic Acid Derivatives / 214 5.9. Allylic and Propargylic Trifluoromethyl Groups / 214 5.9.1. Allylic Trifluoromethyl Groups / 215 5.9.2. , -Unsaturated Carbonyl Compounds / 219 5.9.3. More Heavily Fluorinated Allylics / 222 5.9.4. Propargylic Trifluoromethyl Groups / 222 5.10. Aryl-Bound Trifluoromethyl Groups / 223 5.10.1. Proton and Carbon NMR Data / 224 5.10.2. Multitrifluoromethylated Benzenes / 225 5.11. Heteroaryl-Bound Trifluoromethyl Groups / 228 5.11.1. Pyridines, Quinolines, and Isoquinolines / 228 5.11.2. Pyrimidines and Quinoxalines / 229 5.11.3. Pyrroles and Indoles / 229 5.11.4. Thiophenes and Benzothiophenes / 230 5.11.5. Furans / 230 5.11.6. Imidazoles and Benzimidazoles / 232 5.11.7. Oxazoles, Isoxazoles, Oxazolidines, Thiazoles, 1H-pyrazoles, 1H-indazoles, Benzoxazoles, and Benzothiazoles / 234 5.11.8. Triazoles and Tetrazoles / 235 6 MORE HIGHLY FLUORINATED GROUPS 237 6.1. Introduction / 237 6.2. The 1,1,2- and 1,2,2-Trifluoroethyl Groups / 238 6.3. The 1,1,2,2-Tetrafluoroethyl and 2,2,3,3-Tetrafluoropropyl Groups / 241 6.4. The 1,2,2,2-Tetrafluoroethyl Group / 242 6.5. The Pentafluoroethyl Group / 245 6.5.1. Pentafluoroethyl Carbinols / 248 6.5.2. Pentafluoroethyl Ethers, Sulfides, and Phosphines / 248 6.5.3. Pentafluoroethyl Organometallics / 249 6.6. The 2,2,3,3,3-Pentafluoropropyl Group / 249 6.7. The 1,1,2,3,3,3-Hexafluoropropyl Group / 251 6.8. 1,1,2,2,3,3-Hexafluoropropyl System / 252 6.9. The Hexafluoro-Isopropyl Group / 254 6.10. The Heptafluoro-n-Propyl Group / 255 6.11. The Heptafluoro-iso-Propyl Group / 255 6.12. The Nonafluoro-n-Butyl Group / 255 6.13. The Nonafluoro-iso-Butyl Group / 258 6.14. The Nonafluoro-t-Butyl Group / 258 6.15. Fluorous Groups / 258 6.16. 1-Hydro-Perfluoroalkanes / 259 6.17. Perfluoroalkanes / 260 6.18. Perfluoro-n-Alkyl Halides / 263 6.19. Perfluoroalkyl Amines, Ethers, and Carboxylic Acid Derivatives / 263 6.20. Polyfluoroalkenes / 264 6.20.1. Trifluorovinyl Groups / 264 6.20.2. Perfluoroalkenes / 267 6.21. Polyfluorinated Aromatics / 268 6.21.1. 2,3,5,6-Tetrafluorobenzene Compounds / 268 6.21.2. The Pentafluorophenyl Group / 268 6.22. Polyfluoroheterocyclics / 269 6.22.1. Polyfluoropyridines / 269 6.22.2. Polyfluorofurans / 269 6.22.3. Polyfluorothiophenes / 269 6.22.4. Polyfluoropyrimidines / 271 7 COMPOUNDS AND SUBSTITUENTS WITH FLUORINE DIRECTLY BOUND TO A HETEROATOM 273 7.1. Introduction / 273 7.2. Boron Fluorides / 275 7.3. Fluorosilanes / 275 7.4. Nitrogen Fluorides / 275 7.4.1. Electrophilic Fluorinating Agents / 276 7.5. Phosphorous Fluorides / 277 7.5.1. Phosphorous (III) Fluorides / 277 7.5.2. Phosphorous (V) Fluorides / 277 7.5.3. Phosphorous (V) Oxyfluorides / 280 7.5.4. Cyclophosphazenes / 280 7.6. Oxygen Fluorides (Hypofluorites) / 281 7.7. Sulfur Fluorides / 282 7.7.1. Inorganic Sulfur, Selenium, and Tellurium Fluorides / 282 7.7.2. Diarylsulfur, Selenium, and Tellurium Difluorides / 282 7.7.3. Aryl and Alkyl SF3 Compounds / 283 7.7.4. Dialkylaminosulfur Trifluorides / 283 7.7.5. Hypervalent Sulfur Fluorides / 284 7.7.6. Related Hypervalent Selenium and Tellurium Fluorides / 287 7.7.7. Organic Sulfinyl and Sulfonyl Fluorides / 288 7.8. The Pentafluorosulfanyl (SF5) Group in Organic Chemistry / 289 7.8.1. Saturated Aliphatic Systems / 292 7.8.2. Vinylic SF5 Substituents / 294 7.8.3. Acetylenic SF5 Substituents / 296 7.8.4. Aromatic SF5 Substituents / 297 7.8.5. Heterocyclic SF5 Compounds / 302 7.9. Bromine Trifluoride, Iodine Trifluoride, and Iodine Pentafluoride / 304 7.10. Aryl and Alkyl Halogen Difluorides and Tetrafluorides / 304 7.11. Xenon Fluorides / 305 INDEX 307

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