MODERN FLUOROORGANIC CHEMISTRY
CONTENTS INTRODUCTION WHY ORGANOFLUORINE CHEMISTRY? HISTORY THE BASIC MATERIALS HYDROFLUORIC ACID FLUORINE THE UNIQUE PROPERTIES OF ORGANOFLUORINE COMPOUNDS PHYSICAL PROPERTIES CHEMICAL PROPERTIES ECOLOGICAL IMPACT 1 4 3 1 OZONE DEPLETION BY CHLOROFLUOROCARBONS 1 4 3 2 GREENHOUSE EFFECT PHYSIOLOGICAL PROPERTIES ANALYSIS OF FLUOROCHEMICALS: 19F NMR SPECTROSCOPY SYNTHESIS OF COMPLEX ORGANOFLUORINE COMPOUNDS INTRODUCTION OF FLUORINE PERFLUORINATION AND SELECTIVE DIRECT FLUORINATION ELECTROCHEMICAL FLUORINATION (ECF) NUCLEOPHILIC FLUORINATION 2 1 3 1 FINKELSTEIN EXCHANGE 2 1 3 2 “NAKED” FLUORIDE 2 1 3 3 LEWIS ACID-ASSISTED FLUORINATION 2 1 3 4 THE “GENERAL FLUORINE EFFECT” 2 1 3 5 AMINE–HYDROGEN FLUORIDE AND ETHER–HYDROGEN FLUORIDE REAGENTS 2 1 3 6 HYDROFLUORINATION, HALOFLUORINATION, AND EPOXIDE RING OPENING SYNTHESIS AND REACTIVITY OF FLUOROAROMATIC COMPOUNDS 2 1 4 1 SYNTHESIS OF FLUOROAROMATIC COMPOUNDS 2 1 4 2 REDUCTIVE AROMATIZATION 2 1 4 3 THE BALZ–SCHIEMANN REACTION 2 1 4 4 THE FLUOROFORMATE PROCESS 2 1 4 5 TRANSITION METAL-ASSISTED OXIDATIVE FLUORINATION 2 1 4 6 THE HALEX PROCESS 2 1 4 7 THINK NEGATIVE! – “ORTHOGONAL” REACTIVITY OF PERFLUOROAROMATIC AND PERFLUOROOLEFINIC SYSTEMS 2 1 4 8 THE “SPECIAL FLUORINE EFFECT” 2 1 4 9 AROMATIC NUCLEOPHILIC SUSTITUTION 2 1 4 10 ACTIVATION OF THE CARBON–FLUORINE BOND BY TRANSITION METALS 2 1 4 11 ACTIVATION OF FLUOROAROMATIC COMPOUNDS BY ORTHO-METALATION TRANSFORMATIONS OF FUNCTIONAL GROUPS 2 1 5 1 HYDROXY INTO FLUORO 2 1 5 2 CONVERSION OF CARBONYL INTO GEM-DIFLUOROMETHYLENE 2 1 5 3 CARBOXYL INTO TRIFLUOROMETHYL 2 1 5 4 OXIDATIVE FLUORODESULFURATION “ELECTROPHILIC” FLUORINATION 2 1 6 1 XENON DIFLUORIDE 2 1 6 2 PERCHLORYL FLUORIDE AND HYPOFLUORIDES 2 1 6 3 “NF”-REAGENTS PERFLUOROALKYLATION RADICAL PERFLUOROALKYLATION 2 2 1 1 STRUCTURE, PROPERTIES, AND REACTIVITY OF PERFLUOROALKYL RADICALS 2 2 1 2 PREPARATIVELY USEFUL REACTIONS OF PERFLUOROALKYL RADICALS 2 2 1 3 “INVERSE” RADICAL ADDITION OF ALKYL RADICALS TO PERFLUOROOLEFINS NUCLEOPHILIC PERFLUOROALKYLATION 2 2 2 1 PROPERTIES, STABILITY, AND REACTIVITY OF FLUORINATED CARBANIONS 2 2 2 2 PERFLUOROALKYL METAL COMPOUNDS 2 2 2 3 PERFLUOROALKYL SILANES “ELECTROPHILIC” PERFLUOROALKYLATION 2 2 3 1 PROPERTIES AND STABILITY OF FLUORINATED CARBOCATIONS 2 2 3 2 ARYL PERFLUOROALKYL IODONIUM SALTS 2 2 3 3 PERFLUOROALKYL SULFONIUM, SELENONIUM, TELLURONIUM, AND OXONIUM SALTS DIFLUOROCARBENE AND FLUORINATED CYCLOPROPANES SELECTED FLUORINATED STRUCTURES AND REACTION TYPES DIFLUOROMETHYLATION AND HALODIFLUOROMETHYLATION THE PERFLUOROALKOXY GROUP THE PERFLUOROALKYLTHIO GROUP AND SULFUR-BASED SUPER-ELECTRON- WITHDRAWING GROUPS THE PENTAFLUOROSULFURANYL GROUP AND RELATED STRUCTURES THE CHEMISTRY OF HIGHLY FLUORINATED OLEFINS FLUORINATED POLYMETHINES FLUORINATED ENOL ETHERS AS SYNTHETIC BUILDING BLOCKS FLUOROUS CHEMISTRY FLUOROUS BIPHASE CATALYSIS FLUOROUS SYNTHESIS AND COMBINATORIAL CHEMISTRY FLUOROUS SYNTHESIS SEPARATION ON FLUOROUS STATIONARY PHASES FLUOROUS CONCEPTS IN COMBINATORIAL CHEMISTRY APPLICATIONS OF ORGANOFLUORINE COMPOUNDS HALOFLUOROCARBONS, HYDROFLUOROCARBONS AND RELATED COMPOUNDS POLYMERS AND LUBRICANTS APPLICATIONS IN ELECTRONICS INDUSTRY LIQUID CRYSTALS FOR ACTIVE MATRIX LIQUID CRYSTAL DISPLAYS CALAMITIC LIQUID CRYSTALS: A SHORT INTRODUCTION FUNCTIONING OF ACTIVE MATRIX LCD 4 4 2 1 THE PHYSICAL PROPERTIES OF NEMATIC LIQUID CRYSTALS WHY FLUORINATED LIQUID CRYSTALS? 4 4 3 1 IMPROVED MESOPHASE BEHAVIOR BY LATERAL FLUORINATION 4 4 3 2 FLUORINATED POLAR GROUPS 4 4 3 3 IMPROVED RELIABILITY 4 4 3 4 FLUORINATED BRIDGE STRUCTURES CONCLUSION AND OUTLOOK PHARMACEUTICALS AND OTHER BIOMEDICAL APPLICATIONS WHY FLUORINATED PHARMACEUTICALS? LIPOPHILICITY AND SUBSTITUENT EFFECTS HYDROGEN BONDING AND ELECTROSTATIC INTERACTIONS STEREOELECTRONIC EFFECTS AND CONFORMATION METABOLIC STABILIZATION AND MODULATION OF REACTION CENTERS BIOISOSTERIC MIMICKING MECHANISM-BASED “SUICIDE” INHIBITION FLUORINATED RADIOPHARMACEUTICALS INHALATION ANESTHETICS BLOOD SUBSTITUTES AND RESPIRATORY FLUIDS CONTRAST MEDIA AND MEDICAL DIAGNOSTICS AGRICULTURAL CHEMISTRY