Organic and Inorganic Fluorine Chemistry: Methods and Applications

Description

Organic and Inorganic Fluorine Chemistry provides an introduction to fluorine chemistry and an overview of the most important fluorinated compounds and general preparation techniques. The book is divided into three parts, covering general aspects, inorganic fluorides and fluoroorganic compounds. The inorganic part presents the most important element fluorides and oxyfluorides, their preparation as well as their most characteristic properties. The organic section focuses on the different types of fluorination and the corresponding reagents. The application of these techniques is discussed for many different types of substrates. The book addresses advanced students in chemistry as well as researchers in academia and industry. The readers will benefit from a large number of original references which give access to further information. In addition, study questions at the end of each chapter will help to repeat and internalise the most important aspects. An excellent overview of organic and inorganic fluorine chemistry. Exercises and study questions to each chapter are included. Cover Half Title Also of Interest Organic and Inorganic Fluorine Chemistry: Methods and Applications Copyright Preface Foreword Contents Part A: Introduction to fluorine chemistry 1. Sources of fluorine in nature 1.1 The fluorosphere 1.2 Fluoride sources and elemental fluorine in minerals 1.3 Natural organofluorine compounds 1.4 Study questions 2. Elemental fluorine 2.1 Properties and general reactivity 2.2 Polyfluoride anions 2.3 Preparation of F2 2.4 Working with elemental fluorine and fluorinated compounds 2.5 Study questions 3. Hydrogen fluoride 3.1 Preparation, general properties and applications 3.2 Structural properties 3.3 Anhydrous and aqueous hydrogen fluoride 3.4 Salts of hydrogen fluoride 3.5 Naked fluoride and ligand properties 3.6 Anhydrous hydrogen fluoride as reaction medium 3.7 Study questions 4. Preparation of fluorinated compounds 4.1 Transformations with gaseous fluorinating agents 4.2 Solid-state reactions and fluorinations in flux 4.3 Fluorination in solution phase 4.4 Study questions 5. Common solid-state structures of inorganic fluorides 5.1 Binary fluorides 5.2 Ternary and quaternary fluorides 5.3 Study questions 6. Properties of fluorinated compounds 7. Health and environmental aspects of fluorinated compounds 7.1 Impact of fluorinated compounds on humans and animals 7.2 Fluorinated compounds in the environment 7.3 Perspectives in the use of fluorinated compounds 7.4 Study questions 8. 19F-NMR – an important analytical tool for fluorine chemists 8.1 General aspects and reference substances 8.2 Chemical shifts 8.3 Coupling constants 8.4 Study questions Part B: Inorganic fluorine chemistry 9. Main group element fluorides 9.1 Group 1: Lithium, sodium, potassium, rubidium, cesium 9.1.1 The alkali metal fluorides 9.1.2 Study questions 9.2 Group 2: Beryllium, magnesium, calcium, strontium, barium, radium 9.2.1 Beryllium 9.2.2 Magnesium, calcium, strontium, barium and radium 9.3 Group 13: Boron, aluminium, gallium, indium, thallium 9.3.1 Boron Subfluorides Boron trifluoride and its derivatives 9.3.2 Aluminium, gallium, indium, thallium Monofluorides Trifluorides 9.3.3 Study questions 9.4 Group 14: Carbon, silicon, germanium, tin, lead 9.4.1 Carbon 9.4.2 Silicon, germanium, tin, lead Difluorides Tetrafluorides 9.4.3 Study questions 9.5 Group 15: Nitrogen, phosphorus, arsenic, antimony, bismuth 9.5.1 Nitrogen NF3 and its derivatives Tetrafluorohydrazine and difluorodiazene Tetrafluoroammonium salts Fluoroazide Oxyfluorides of nitrogen 9.5.2 Phosphorus, arsenic, antimony, bismuth Diphosphorus tetrafluoride Trifluorides Pentafluorides and their derivatives 9.5.3 Study questions 9.6 Group 16: Oxygen, sulphur, selenium, tellurium, polonium 9.6.1 Oxygen Oxygen fluorides Inorganic hypofluorites Organic hypofluorites 9.6.2 Sulphur, selenium, tellurium, polonium Low-valent fluorides Tetrafluorides and tetravalent oxyfluorides Hexafluorides and hexavalent oxyfluorides Sulphur-nitrogen-fluorine compounds 9.6.3 Study questions 9.7 Group 17: Chlorine, bromine, iodine 9.7.1 Preparation of the halogen fluorides 9.7.2 Structural properties of the halogen fluorides 9.7.3 Stability of the halogen fluorides 9.7.4 Reactivity of the halogen fluorides 9.7.5 Fluorinated cations derived from the halogen fluorides 9.7.6 Fluorohalogenate anions 9.7.7 Halogen oxyfluorides Trivalent compounds Pentavalent compounds Heptavalent compounds 9.8 Group 18: Krypton, xenon, radon 9.8.1 Xenon Xenon difluoride Xenon tetrafluoride Xenon hexafluoride General conclusions on the reactivity of xenon fluorides Derivatives of the xenon fluorides Xenon oxyfluorides 9.8.2 Krypton 9.8.3 Radon 9.8.4 Study questions 10. Transition metal fluorides and rare earth metal fluorides 10.1 Group 3: Scandium, yttrium, lanthanum, actinium 10.1.1 Compounds and properties Low-valent fluorides Trifluorides Oxyfluorides 10.1.2 Study question 10.2 The lanthanides 10.2.1 Compounds and properties Monofluorides Difluorides Trifluorides Tetrafluorides 10.2.2 Study questions 10.3 The actinides 10.3.1 Compounds and properties Mono- and difluorides Trifluorides and trivalent oxyfluorides Tetrafluorides and tetravalent oxyfluorides Pentafluorides and pentavalent oxyfluorides Hexafluorides 10.3.2 Study questions 10.4 Group 4: Titanium, zirconium, hafnium 10.4.1 Titanium Titanium trifluoride Titanium tetrafluoride Titanium oxydifluoride 10.4.2 Zirconium and hafnium Low-valent fluorides Trifluorides Tetrafluorides 10.4.3 Study questions 10.5 Group 5: Vanadium, niobium, tantalum 10.5.1 Vanadium Low-valent fluorides Vanadium trifluoride Vanadium tetrafluoride Vanadium pentafluoride Pentavalent vanadium oxyfluorides 10.5.2 Niobium and tantalum Low-valent fluorides Trifluorides Tetrafluorides Pentafluorides Pentavalent oxyfluorides 10.5.3 Study questions 10.6 Group 6: Chromium, molybdenum, tungsten 10.6.1 Chromium Chromium trifluoride Chromium tetrafluoride Chromium pentafluoride Chromium hexafluoride and hexavalent oxyfluorides of chromium 10.6.2 Molybdenum and tungsten Low-valent fluorides Trifluorides Tetrafluorides Pentafluorides Hexafluorides Hexavalent oxyfluorides 10.6.3 Study questions 10.7 Group 7: Manganese, technetium, rhenium 10.7.1 Manganese Low-valent manganese fluorides Manganese trifluoride Manganese tetrafluoride Manganese oxyfluorides 10.7.2 Technetium and rhenium Low-valent fluorides Trifluorides Tetrafluorides Hexafluorides Hexavalent oxyfluorides Heptafluorides Heptavalent oxyfluorides 10.7.3 Study questions 10.8 Iron, cobalt, nickel 10.8.1 Compounds and properties Monofluorides Difluorides Trifluorides Complexes derived from the trifluorides Tetrafluorides and fluorometallates(IV) 10.8.2 Study questions 10.9 The platinum metals: ruthenium, osmium, rhodium, iridium, platinum 10.9.1 Compounds and properties Monofluorides Difluorides Trifluorides Tetrafluorides Hexafluorides Hexavalent oxyfluorides Heptavalent oxyfluorides Octavalent oxyfluorides 10.9.2 Study questions 10.10 Group 11: Copper, silver, gold 10.10.1 Copper Copper monofluoride Copper difluoride Copper trifluoride and tetravalent compounds 10.10.2 Silver Silver subfluoride Silver monofluoride Silver difluoride Silver trifluoride 10.10.3 Gold Low-valent gold fluorides Gold trifluoride High-valent gold fluorides 10.10.4 Study questions 10.11 Group 12: Zinc, cadmium, mercury 10.11.1 Zinc 10.11.2 Cadmium 10.11.3 Mercury Dimercury difluoride Mercury difluoride 10.11.4 Zinc, cadmium and mercury in higher oxidation states 10.11.5 Study questions Part C: Organic fluorine chemistry 11. Fluoroorganic compounds – unusual properties and versatile applications 11.1 Physical properties of fluoroorganic compounds 11.1.1 Boiling points and dipole moments 11.1.2 Solvent properties 11.1.3 Surface tension and surface energy 11.1.5 Acidity and basicity 11.1.4 Lipophilicity 11.1.6 Study questions 11.2 Chemical properties and stability of fluoroorganic compounds and reactive intermediates 11.2.1 Fluorine at sp3-carbons 11.2.2 Fluorine at sp2-and sp-carbons 11.2.3 Fluorinated carbocations 11.2.4 Fluorinated carbanions 11.2.5 Fluorinated radicals 11.2.6 Fluorinated carbenes 11.2.7 Study questions 11.3 Applications of organofluorine compounds 11.3.1 Versatile uses of halo- and hydrofluorocarbons 11.3.2 Fluoropolymers 11.3.3 Fluorinated dyes 11.3.4 Fluorinated liquid crystals 11.3.5 Organic electronics 11.3.6 Biologically active compounds 11.3.7 Medicinal diagnostics 11.3.8 Further medical applications 11.3.9 Study questions 12. General reaction types and reagents for the introduction of fluorin 12.1 Direct fluorination and radical reactions 12.1.1 Elemental fluorine and high-valent metal fluorides 12.1.2 Radical fluorination using electrophilic fluorinating reagents 12.1.3 Study questions 12.2 Electrochemical fluorination 12.2.1 Prerequisites 12.2.2 Mechanistical aspects 12.3 Nucleophilic fluorination 12.3.1 HF and its complexes 12.3.2 Ionic fluorides Metal fluorides Tetraalkylammonium fluorides Other salt-like sources of fluoride 12.3.3 Molecular fluorides Inorganic main-group element fluorides α,α-Difluoroalkylamine reagents 12.3.4 Enzymatic fluorination 12.3.5 Study questions 12.4 Electrophilic fluorination 12.4.1 Fluoroxy compounds, perchloryl fluoride and xenon difluoride 12.4.2 Fluoraza reagents 12.4.3 Study questions 12.5 Metal-mediated reactions, including photocatalysis 12.6 Hydrodefluorination and defluorofunctionalization 13. Fluorination of aliphatic substrates 13.1 General trends in the synthesis of aliphatic organofluorine compounds 13.1.1 The general fluorine effect 13.1.2 The special fluorine effect 13.1.3 Study questions 13.2 Radical reactions and direct fluorination 13.2.1 General remarks on direct fluorination techniques 13.2.2 Direct fluorination techniques using elemental F2 13.2.3 Fluorination using high-valent metal fluorides 13.2.4 Selective radical fluorination with electrophilic fluorinating agents Techniques using catalytic and stoichiometric radical initiators Photocatalysis 13.2.5 Study questions 13.3 Electrochemical fluorination techniques 13.3.1 Conditions and substrates 13.3.2 Cyclization of carbonyl compounds 13.3.3 Electrochemical fluorination of heteroatom-containing substrates 13.3.4 Study questions 13.4 Nucleophilic substitution 13.4.1 Halogen exchange Halogen fluorides as fluorinating agents Fluoride salts, HF-reagents or antimony fluorides as fluorinating agents 13.4.2 Deoxyfluorination of alcohols HF-reagents and other acidic fluoride sources Fluoroalkylamine reagents Sulphur(IV)-based deoxyfluorinating agents Fluorodehydroxylation of activated alcohol functions 13.4.3 Cleavage of ethers and epoxides 13.4.4 Deoxyfluorination of carbonyl compounds 13.4.5 Deoxyfluorination of carboxylic acids and their derivatives 13.4.6 Sulphur replacement 13.4.7 Nitrogen replacement 13.4.8 Hydrofluorination of unsaturated C-C bonds 13.4.9 Halofluorination of unsaturated C-C bonds 13.4.10 Fluorocarbene addition to unsaturated C-C bonds 13.4.11 Halo- and hydrofluorination of highly fluorinated olefins 13.4.12 Highly fluorinated olefins as building blocks 13.4.13 Study questions 13.5 Electrophilic fluorination 13.5.1 Elemental fluorine as electrophilic fluorinating agent 13.5.2 Electrophilic fluorination using fluoroxy compounds 13.5.3 Electrophilic fluorination using perchloryl fluoride 13.5.4 Fluoraza compounds as electrophilic fluorinating agents 13.5.5 Asymmetric fluorination using fluoraza reagents 13.5.6 Xenon difluoride 13.5.7 Study questions 13.6 Metal-mediated reactions, including photocatalysis 13.6.1 C-H fluorination Directing-group approaches Enantioselective C-H fluorination of activated substrates Radical fluorination using electrophilic fluorinating agents Photocatalytic fluorination Radical fluorination in presence of directing groups Radical fluorination using nucleophilic fluorinating agents 13.6.2 Fluorofunctionalization of olefins 13.6.3 Allylic, benzylic and propargylic substrates with a leaving group 13.6.4 Study questions 13.7 Selected transformations of fluorinated compounds 13.7.1 Reductive transformations 13.7.2 Oxidative transformations 13.7.3 Halogenations 13.7.4 Study questions 14. Fluorination of (hetero-) aromatic compounds 14.1 Electrochemical fluorination techniques 14.2 Nucleophilic substitution 14.2.1 Halogen exchange 14.2.2 Fluorodenitration and fluorodesulphonylation 14.2.3 Preparation of pentafluorophenyl compounds 14.2.4 Deoxyfluorination The fluoroformate process Direct deoxyfluorination of phenols 14.2.5 Nitrogen replacement Decompositon of aryl diazonium salts Decomposition of aryl triazenes Fluorodequaternization 14.2.6 Miscellaneous transformations 14.2.7 Study questions 14.3 Electrophilic fluorination 14.3.1 Elemental fluorine as electrophilic fluorinating agent 14.3.2 Electrophilic fluorination using fluorooxy reagents 14.3.3 Xenon difluoride as a source of electrophilic fluorine 14.3.4 Electrophilic fluorination using fluoraza reagents 14.3.5 Study questions 14.4 Reductive aromatization 14.5 Metal-mediated reactions 14.5.1 Reactions mediated by palladium General aspects about Pd-mediated fluorination reactions Pd(II)-mediated C-H fluorination in presence of directing groups Pd(0)-mediated fluorination Miscellaneous variants of Pd-catalyzed fluorination 14.5.2 Reactions mediated by copper 14.5.3 Reactions mediated by silver 14.5.4 Reactions mediated by bismuth 14.5.5 Study questions 14.6 C-F bond activation 14.6.1 Replacement of fluoride substituents in highly fluorinated aromat 14.6.2 Fluoride replacement by main-group organometallics 14.6.3 C-F bond activation by transition metal complexes Hydrodefluorination Formation of carbon-heteroatom bonds 14.6.4 Study questions 15. Preparation of fluorinated olefins and acetylenes 15.1 Elimination reactions 15.1.1 Elimination of HX 15.1.2 Elimination of HF 15.1.3 Elimination of halogens 15.1.4 Elimination of other small molecules 15.1.5 Pyrolysis of fluorinated compounds 15.1.6 Preparation of fluorine-containing polyenes 15.1.7 Fluorinated acetylenes 15.2 Nucleophilic substitution 15.2.1 Nucleophilic attack on CF3-substituted vinyl compounds 15.2.2 Addition-elimination reactions of fluorinated olefins 15.2.3 Miscellaneous reactions toward fluoroolefins 15.2.4 Study questions 15.3 Electrophilic fluorination 15.3.1 Fluorination of vinyl lithium intermediates 15.3.2 Electrophilic fluorination of substituted cyclopropanes and allenes 15.3.3 Miscellaneous transformations 15.3.4 Study questions 15.4 Transition metal-free introduction of fluorinated fragments 15.4.1 Wittig olefination 15.4.2 Julia- and Julia–Kocienski-type olefinations 15.4.3 Horner–Wadsworth–Emmons olefination 15.5 Olefin metathesis 15.5.1 General aspects about metathesis reactions of fluorinated olefins 15.5.2 Preparation of fluorinated carbocycles 15.5.3 Preparation of fluorinated heterocycles 15.5.4 Study questions 15.6 Metal-mediated reactions, including photocatalysis 15.6.1 Hydrofluorination of alkynes 15.6.2 Directed C-H fluorination of vinylic substrates 15.6.3 Fluorination of vinyl boronic acids and vinyl stannanes 15.6.4 Miscellaneous transformations toward monofluoroolefins 15.6.5 Preparation of geminal difluoroolefins from CF3-substituted alkenes 15.6.6 Preparation of geminal difluoroolefins from diazocompounds 15.6.7 Study questions 15.7 Selective hydrodefluorination of highly fluorinated olefins 16. Solutions to study questions Bibliography Index