Efficient Preparations of Fluorine Compounds

The definitive guide to creating fluorine-based compounds?and the materials of tomorrowDiscovered as an element by the French chemist Henri Moissan in 1886, through electrolysis of potassium fluoride in anhydrous hydrogen fluoride?"le fluor," or fluorine, began its chemical history as a substance both elusive and dangerous. With a slight pale yellow hue, fluorine is at room temperature a poisonous diatomic gas. Resembling a spirit from a chemical netherworld, fluorine is highly reactive, difficult to handle, yet very versatile as a reagent?with the power to form compounds with almost any other element.Comprising 20% of pharmaceutical products and 30% of agrochemical compounds, as well as playing a key role in electric cars, electronic devices, and space technology, compounds containing fluorine have grown in importance across the globe. Learning how to safely handle fluorine in the preparation of innovative new materials?with valuable new properties?is of critical importance to chemists today. Bringing together the research and methods of leading scientists in the fluorine field, Efficient Preparations of Fluorine Compounds is the definitive manual to creating, and understanding the reaction mechanisms integral to a wide variety of fluorine compounds. With sixty-eight contributed chapters, the book's extensive coverage includes:Preparation of Elemental FluorineSynthesis Methods for Exotic Inorganic Fluorides with Varied ApplicationsIntroduction of Fluorine into Compounds via Electrophilic and Nucleophilic ReactionsDirect Fluorination of Organic Compounds with Elemental FluorineEfficient Preparations of Bioorganic Fluorine CompoundsAsymmetric Fluorocyclization ReactionsPreparations of Rare Earth Fluorosulfides and OxyfluorosulfidesThe book offers methods and results that can be reproduced by students involved in advanced studies, as well as practicing chemists, pharmaceutical scientists, biologists, and environmental researchers. The only chemical resource of its kind, Efficient Preparations of Fluorine Compounds?from its first experiment to its last?is a unique window into the centuries old science of fluorine and the limitless universe of fluorine-based compounds.Content: Chapter 1 Preparation of Elemental Fluorine (pages 1–6): Karl O. ChristeChapter 2 Preparation of Highly Active Cesium Fluoride (pages 7–8): Konrad SeppeltChapter 3 Preparation of Highly Active Silver Fluoride (pages 9–10): Konrad SeppeltChapter 4 A Room?Temperature Non?Irradiative Synthesis of XeF2 (pages 11–15): Ulf Breddemann, John R. Debackere and Gary J. SchrobilgenChapter 5 Efficient Perfluorination of K2B12H12 in Neutral Acetonitrile (pages 16–18): Dmitry V. Peryshkov, Eric V. Bukovsky and Steven H. StraussChapter 6 Efficient Preparation of the Highly Soluble ortho? and para?C60(CF2C6F5)2 Derivatives (pages 19–21): Igor V. Kuvychko, Bryon W. Larson, Steven H. Strauss and Olga V. BoltalinaChapter 7 Synthesis of Cs[1?H?CB11F11] (pages 22–25): Michal Valasek, Filip sembera, Michael J. Hughes, Ivan Stibor, Zbynek Janousek and Josef MichlChapter 8 Synthesis of Zero?Valent Trifluoromethyl Chalcogenato Derivatives, [NMe4]ECF3 (E = S, Se, Te), and Related Compounds (pages 26–34): Wieland Tyrra and Silke KremerChapter 9 Synthesis Methods for Exotic Inorganic Fluorides with Varied Applications (pages 35–59): Dayal T. Meshri, N. C. Mathur and Ritesh R. JainChapter 10 Tris(pentafluorophenyl)borane, B(C6F5)3, a Powerful, Well?Soluble, Nonoxidizing Lewis Acid and the Weakly Coordinating Tetrakis(pentafluorophenyl)borate Anion, [B(C6F5)4]? (pages 60–64): Hermann?Josef FrohnChapter 11 Pentafluorophenyldifluoroborane, C6F5BF2, and Pentafluorophenyltrifluorosilane, C6F5SiF3, Versatile Reagents for Fluorine/Pentafluorophenyl Substitution Reactions in Strongly Oxidizing Hypervalent Nonmetal Fluorides (pages 65–71): Hermann?Josef FrohnChapter 12 Iodine(III and V) Fluorides: Interesting Fluorinating Agents (pages 72–75): Hermann?Josef FrohnChapter 13 Tetramethylammonium Fluoride, [N(CH3)4]F, a Widely Applicable Reagent to Introduce Fluoride Ions and a Suitable Nucleophile to Initiate the Transfer of Perfluoroorganyl Groups to Electrophiles (pages 76–78): Hermann?Josef FrohnChapter 14 Preparation of Transition Metal Sulfide Fluorides (pages 79–81): Michael GerkenChapter 15 Transition Metal Carbonyl Sulfur Dioxide and Thiazylfluoride Complexes: Reactions at the Metal Center and at the Ligand (pages 82–87): Rudiger MewsChapter 16 Cesium, Mercury, and Silver Salts with Sulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks (pages 88–93): Rudiger MewsChapter 17 Laboratory?Scale Synthesis of Gold Trifluoride and Uranium Hexafluoride (pages 94–99): Thomas M. KlapotkeChapter 18 Preparation of Transition Metal Fluorides using ClF3 (pages 100–107): Ralf HaigesChapter 19 Preparation of Fluorine?Containing Molecular Halides and Heteropolar Salts with Elements of Group 15 and Niobium and Tantalum Halides (pages 108–116): Lothar KolditzChapter 20 Fluoro and Fluorohydroxy Complexes of As, Sb, and Sn (pages 117–120): Lothar KolditzChapter 21 Trifluoromethyl Compounds via Electrophilic and Nucleophilic Reactions (pages 121–126): Jean'ne M. ShreeveChapter 22 Introduction of Fluorine into Compounds via Electrophilic and Nucleophilic Reactions (pages 127–132): Jean'ne M. ShreeveChapter 23 The “Real” Iodine and Bromine Monofluorides (pages 133–138): Shlomo RozenChapter 24 The Versatile Chemistry of Acetyl Hypofluorite: The First Hypofluorite Not Bonded to a Polyhaloalkyl Group (pages 139–145): Shlomo RozenChapter 25 Direct Fluorination of Organic Compounds with Elemental Fluorine (pages 146–153): Shlomo RozenChapter 26 The Surprising Chemistry of Bromine Trifluoride (pages 154–172): Shlomo RozenChapter 27 Preparation of Silicon? and Sulfur?Based Fluorinated Methane Derivatives as Versatile Fluoromethylation Reagents (pages 173–204): G. K. Surya Prakash and Fang WangChapter 28 Pentafluoroethyl Lithium: Reactions with Carbonyl Compounds and Epoxides (pages 205–209): Olesya Kazakova and Gerd?Volker RoschenthalerChapter 29 Synthesis of ??Hydroxy??,??difluoromethylenephosphonates (pages 210–213): Olesya Kazakova and Gerd?Volker RoschenthalerChapter 30 Synthesis of Pentafluoro??6?sulfanyl?Substituted Acetylenes for Liquid Crystals (pages 214–219): Olesya Kazakova, Maxim Ponomarenko and Gerd?Volker RoschenthalerChapter 31 Delocalized Lipophilic Cations as a Source of Naked Fluoride and Phase?Transfer Catalysts (pages 220–226): Nataliya Kalinovich, Olesya Kazakova and Gerd?Volker RoschenthalerChapter 32 Methyltrifluoropyruvate Imines Possessing N?oxalyl and N?Phosphonoformyl Groups: Precursors to a Variety of ??CF3???Amino Acid Derivatives (pages 227–231): Olesya Kazakova and Gerd?Volker RoschenthalerChapter 33 Rhodium?Mediated Synthesis of (3,3,3?Trifluoropropyl)trimethoxysilane and (3,3,3?Trifluoropropyl)triphenylsilane (pages 232–234): Falk Wehmeier and Thomas BraunChapter 34 Rhodium?Mediated Synthesis of a Tetrafluoropyridyl?2?boronate Ester (pages 235–236): Michael Teltewskoi and Thomas BraunChapter 35 Palladium?Mediated Synthesis of 4?Vinyltetrafluoropyridine and 2,3,5,6?Tetrafluoropyridine (pages 237–239): David Breyer and Thomas BraunChapter 36 Preparation of Polyfluoroaryl?1,2?difluorovinylsilanes (pages 240–242): Donald J. Burton and Ba V. NguyenChapter 37 Preparation of (Z)?2?iodo?1,2?Difluorostyrenes (pages 243–245): Donald J. Burton and Ling XueChapter 38 Preparation of 1,4?Bis(Z?2?iodo?1,2?difluoroethenyl)benzene (pages 246–247): Donald J. Burton and Craig A. WesolowskiChapter 39 Stereospecific Carboamidation Route to (Z)?N?Phenyl?2,3?difluoro?3?(triethylsilyl) acrylamide (pages 248–249): Donald J. Burton and Craig A. WesolowskiChapter 40 Preparation of 2?Trifluoromethyl?3,3,3?trifluoropropanal (pages 250–251): Donald J. Burton and Donald A. WiebeChapter 41 Synthesis of Tetrafluorocatechol (pages 252–255): Sudharsanam Ramanathan, Dayong Sang, Vivek Kumar and David M. LemalChapter 42 Preparation of an Unsymmetrical Bis((perfluoroalkyl)sulfonyl)imide (pages 256–261): Darryl D. DesMarteau and Thomas D. HickmanChapter 43 Preparation of Perfluoroalkyl Sulfilimines and Sulfoximines (pages 262–265): Emmanuel MagnierChapter 44 Preparation of Trifluoromethylsulfonium Salts (pages 266–269): Emmanuel MagnierChapter 45 Preparation of Organometallic Fluorides of Main Group and Transition Elements (pages 270–274): Herbert W. RoeskyChapter 46 Preparation of Pentafluorosulfanyl Carbonyl Compounds (pages 275–278): John T. WelchChapter 47 Preparation of Power?Variable Electrophilic Trifluoromethylating Agents, S?(Trifluoromethyl)dibenzothiophenium Salts Series (pages 279–289): Teruo UmemotoChapter 48 Synthesis of Fluorine?Containing Heterocycles from ?,??Dihydropolyfluoroalkylsulfides and Fluorinated Thiocarboxylic Acids Derivatives (pages 290–307): Vadim M. Timoshemko and Yuriy G. ShermolovichChapter 49 Synthesis of Octafluorocyclooctatetraene (pages 308–314): John M. Buzby, Aldos C. Barefoot, Michael W. Grayston, Evan D. Laganis, Roy F. Waldron and David M. LemalChapter 50 Preparation of Fluoroolefins (pages 315–333): Moritz F. Kuehnel and Dieter LentzChapter 51 Preparation of Ionic Liquids of Fluorocomplex and Oxofluorocomplex Anions by Fluoroacid–Base Reactions (pages 334–337): Kazuhiko Matsumoto and Rika HagiwaraChapter 52 Synthesis of Difluorocyclopropyl Building Blocks: 2,2?Difluorocyclopropylmethanol and 2?(Bromomethyl)?1,1?difluorocyclopropane (pages 338–342): Wei Xu and William R. DolbierChapter 53 Preparation of 1,1,2,2,9,9,10,10?Octafluoro[2.2]paracyclophane and Perfluoro[2.2]paracyclophane (pages 343–348): William R. Dolbier, Jian?Xi Duan, Alex J. Roche and Lianhao ZhangChapter 54 Synthesis and Application of gem?Difluoromethylenated and Trifluoromethylated Building Blocks (pages 349–364): Feng?Ling Qing and Xiao?Long QiuChapter 55 1,3?Dipolar Cycloaddition Reactions to Fluoroalkenes (pages 365–369): Hanna Wojtowicz?Rajchel and Henryk KoroniakChapter 56 Synthesis of Fluorinated Vinyl Derivatives of Nucleic Acid Bases (pages 370–374): Hanna Wojtowicz?Rajchel, Donata Pluskota?Karwatka and Henryk KoroniakChapter 57 Synthesis of CF3?Substituted Aziridine Ring by the Gabriel Reaction (pages 375–378): Tomasz Cytlak, Bartosz Marciniak and Henryk KoroniakChapter 58 Preparation of ??Fluoro Amino and ??Fluoro Enamino Reagents (pages 379–384): Justyna Walkowiak and Henryk KoroniakChapter 59 Synthesis of Original Fluoromonomers and Their Radical Copolymerization with Vinylidene Fluoride (pages 385–395): Bruno AmeduriChapter 60 Convergent 18F Radiosynthesis (pages 396–399): V. Gouverneur and O. LozanoChapter 61 Asymmetric Fluorocyclization Reactions (pages 400–404): V. Gouverneur and O. LozanoChapter 62 Preparation of Allylic Fluorides (pages 405–411): V. Gouverneur and O. LozanoChapter 63 Dehydroxyfluorinations of Primary or Secondary Alcohols Using Perfluoro n?Butylsulfonyl Fluoride (Nonaflyl Fluoride) in Combination with 1,8?Diaza?bicyclo[5.4.0]undec?7?ene (pages 412–414): Orlin Petrov, Matthias Schneider, Rolf Bohlmann, Stephan Vettel and Helmut VorbruggenChapter 64 Preparation of Rare Earth Fluorosulfides and Oxyfluorosulfides (pages 415–424): A. Demourgues and A. TressaudChapter 65 Preparation of Carbon–Fluorine Compounds and Fluoride or Oxide Fluoride?Intercalated Graphites (pages 425–432): Tsuyoshi NakajimaChapter 66 Safe Synthesis of Superstoichiometric Mesoporous Fluorocarbons (pages 433–441): Valentin N. MitkinChapter 67 Preparation of Fluorinated ??Alumina (pages 442–446): Erhard Kemnitz, Tomaz Skapin and John M. WinfieldChapter 68 High?Yield Synthesis of a Single Asymmetric Isomer of C70(CF3)10 by High?Temperature Radical Trifluoromethylation (pages 447–449): Natalia B. Shustova, Steven H. Strauss and Olga V. Boltalina