Efficient Preparations of Fluorine Compounds

The definitive guide to creating fluorine-based compounds—and the materials of tomorrow Discovered 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 Fluorine Synthesis Methods for Exotic Inorganic Fluorides with Varied Applications Introduction of Fluorine into Compounds via Electrophilic and Nucleophilic Reactions Direct Fluorination of Organic Compounds with Elemental Fluorine Efficient Preparations of Bioorganic Fluorine Compounds Asymmetric Fluorocyclization Reactions Preparations of Rare Earth Fluorosulfides and Oxyfluorosulfides The 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.

Table of Contents:
Foreword xi Preface xiii Contributors xv 1 Preparation of Elemental Fluorine 1 Karl O. Christe 2 Preparation of Highly Active Cesium Fluoride 7 Konrad Seppelt 3 Preparation of Highly Active Silver Fluoride 9 Konrad Seppelt 4 A Room-Temperature Non-Irradiative Synthesis of XeF2 11 Ulf Breddemann, John R. DeBackere, and Gary J. Schrobilgen 5 Efficient Perfluorination of K2B12H12 in Neutral Acetonitrile 16 Dmitry V. Peryshkov, Eric V. Bukovsky, and Steven H. Strauss 6 Efficient Preparation of the Highly Soluble ortho- and para-C60(CF2C6F5)2 Derivatives 19 Igor V. Kuvychko, Bryon W. Larson, Steven H. Strauss, and Olga V. Boltalina 7 Synthesis of Cs[1-H-CB11F11] 22 Michal Vala¡sek, Filip Šembera, Michael J. Hughes, Ivan Stibor, Zbyn¡ek Janou¡sek, and Josef Michl 8 Synthesis of Zero-Valent Trifluoromethyl Chalcogenato Derivatives, [NMe4]ECF3 (E = S, Se, Te), and Related Compounds 26 Wieland Tyrra and Silke Kremer 9 Synthesis Methods for Exotic Inorganic Fluorides with Varied Applications 35 Dayal T. Meshri, N. C. Mathur, and Ritesh R. Jain 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]− 60 Hermann-Josef Frohn 11 Pentafluorophenyldifluoroborane, C6F5BF2, and Pentafluorophenyltrifluorosilane, C6F5SiF3, Versatile Reagents for Fluorine/Pentafluorophenyl Substitution Reactions in Strongly Oxidizing Hypervalent Nonmetal Fluorides 65 Hermann-Josef Frohn 12 Iodine(III and V) Fluorides: Interesting Fluorinating Agents 72 Hermann-Josef Frohn 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 76 Hermann-Josef Frohn 14 Preparation of Transition Metal Sulfide Fluorides 79 Michael Gerken 15 Transition Metal Carbonyl Sulfur Dioxide and Thiazylfluoride Complexes: Reactions at the Metal Center and at the Ligand 82 Rudiger Mews 16 Cesium, Mercury, and Silver Salts with Sulfur-Nitrogen-Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks 88 Rudiger Mews 17 Laboratory-Scale Synthesis of Gold Trifluoride and Uranium Hexafluoride 94 Thomas M. Klapotke 18 Preparation of Transition Metal Fluorides using ClF3 100 Ralf Haiges 19 Preparation of Fluorine-Containing Molecular Halides and Heteropolar Salts with Elements of Group 15 and Niobium and Tantalum Halides 108 Lothar Kolditz 20 Fluoro and Fluorohydroxy Complexes of As, Sb, and Sn 117 Lothar Kolditz 21 Trifluoromethyl Compounds via Electrophilic and Nucleophilic Reactions 121 Jeanne M. Shreeve 22 Introduction of Fluorine into Compounds via Electrophilic and Nucleophilic Reactions 127 Jeanne M. Shreeve 23 The "Real" Iodine and Bromine Monofluorides 133 Shlomo Rozen 24 The Versatile Chemistry of Acetyl Hypofluorite: The First Hypofluorite Not Bonded to a Polyhaloalkyl Group 139 Shlomo Rozen 25 Direct Fluorination of Organic Compounds with Elemental Fluorine 146 Shlomo Rozen 26 The Surprising Chemistry of Bromine Trifluoride 154 Shlomo Rozen 27 Preparation of Silicon- and Sulfur-Based Fluorinated Methane Derivatives as Versatile Fluoromethylation Reagents 173 G.K. Surya Prakash and Fang Wang 28 Pentafluoroethyl Lithium: Reactions with Carbonyl Compounds and Epoxides 205 Olesya Kazakova and Gerd-Volker Roschenthaler 29 Synthesis of gamma-Hydroxy-gamma, gamma-difluoromethylenephosphonates 210 Olesya Kazakova and Gerd-Volker Roschenthaler 30 Synthesis of Pentafluoro-gamma6-sulfanyl-Substituted Acetylenes for Liquid Crystals 214 Olesya Kazakova, Maxim Ponomarenko, and Gerd-Volker Roschenthaler 31 Delocalized Lipophilic Cations as a Source of Naked Fluoride and Phase-Transfer Catalysts 220 Nataliya Kalinovich, Olesya Kazakova, and Gerd-Volker Roschenthaler 32 Methyltrifluoropyruvate Imines Possessing N-oxalyl and N-Phosphonoformyl Groups: Precursors to a Variety of Alpha-CF3-Alpha-Amino Acid Derivatives 227 Olesya Kazakova and Gerd-Volker Roschenthaler 33 Rhodium-Mediated Synthesis of (3,3,3-Trifluoropropyl)trimethoxysilane and (3,3,3-Trifluoropropyl)triphenylsilane 232 Falk Wehmeier and Thomas Braun 34 Rhodium-Mediated Synthesis of a Tetrafluoropyridyl-2-boronate Ester 235 Michael Teltewskoi and Thomas Braun 35 Palladium-Mediated Synthesis of 4-Vinyltetrafluoropyridine and 2,3,5,6-Tetrafluoropyridine 237 David Breyer and Thomas Braun 36 Preparation of Polyfluoroaryl-1,2-difluorovinylsilanes 240 Donald J. Burton and Ba V. Nguyen 37 Preparation of (Z)-2-iodo-1,2-difluorostyrenes 243 Donald J. Burton and Ling Xue 38 Preparation of 1,4-Bis(Z-2-iodo-1,2-difluoroethenyl)benzene 246 Donald J. Burton and Craig A. Wesolowski 39 Stereospecific Carboamidation Route to (Z)-N-Phenyl-2,3-difluoro-3-(triethylsilyl) acrylamide 248 Donald J. Burton and Craig A. Wesolowski 40 Preparation of 2-Trifluoromethyl-3,3,3-trifluoropropanal 250 Donald J. Burton and Donald A. Wiebe 41 Synthesis of Tetrafluorocatechol 252 Sudharsanam Ramanathan, Dayong Sang, Vivek Kumar, and David M. Lemal 42 Preparation of an Unsymmetrical Bis((perfluoroalkyl)sulfonyl)imide 256 Darryl D. Desmarteau and Thomas D. Hickman 43 Preparation of Perfluoroalkyl Sulfilimines and Sulfoximines 262 Emmanuel Magnier 44 Preparation of Trifluoromethylsulfonium Salts 266 Emmanuel Magnier 45 Preparation of Organometallic Fluorides of Main Group and Transition Elements 270 Herbert W. Roesky 46 Preparation of Pentafluorosulfanyl Carbonyl Compounds 275 John T. Welch 47 Preparation of Power-Variable Electrophilic Trifluoromethylating Agents, S-(Trifluoromethyl)dibenzothiophenium Salts Series 279 Teruo Umemoto 48 Synthesis of Fluorine-Containing Heterocycles from alpha,alpha-Dihydropolyfluoroalkylsulfides and Fluorinated Thiocarboxylic Acids Derivatives 290 Vadim M. Timoshemko and Yuriy G. Shermolovich 49 Synthesis of Octafluorocyclooctatetraene 308 John M. Buzby, Aldos C. Barefoot, III, Michael W. Grayston, Evan D. Laganis, Roy F. Waldron, and David M. Lemal 50 Preparation of Fluoroolefins 315 Moritz F. Kuhnel and Dieter Lentz 51 Preparation of Ionic Liquids of Fluorocomplex and Oxofluorocomplex Anions by Fluoroacid–Base Reactions 334 Kazuhiko Matsumoto and Rika Hagiwara 52 Synthesis of Difluorocyclopropyl Building Blocks: 2,2-Difluorocyclopropylmethanol and 2-(Bromomethyl)-1,1-difluorocyclopropane 338 Wei Xu and William R. Dolbier Jr. 53 Preparation of 1,1,2,2,9,9,10,10-Octafluoro[2.2]paracyclophane and Perfluoro[2.2]paracyclophane 343 William R. Dolbier Jr., Jian-Xi Duan, Alex J. Roche, and Lianhao Zhang 54 Synthesis and Application of gem-Difluoromethylenated and Trifluoromethylated Building Blocks 349 Feng-Ling Qing and Xiao-Long Qiu 55 1,3-Dipolar Cycloaddition Reactions to Fluoroalkenes 365 Hanna Wojtowicz-Rajchel and Henryk Koroniak 56 Synthesis of Fluorinated Vinyl Derivatives of Nucleic Acid Bases 370 Hanna Wojtowicz-Rajchel, Donata Pluskota-Karwatka, and Henryk Koroniak 57 Synthesis of CF3-Substituted Aziridine Ring by the Gabriel Reaction 375 Tomasz Cytlak, Bartosz Marciniak, and Henryk Koroniak 58 Preparation of alpha-Fluoro Amino and alpha-Fluoro Enamino Reagents 379 Justyna Walkowiak and Henryk Koroniak 59 Synthesis of Original Fluoromonomers and Their Radical Copolymerization with Vinylidene Fluoride 385 Bruno Ameduri 60 Convergent 18F Radiosynthesis 396 V. Gouverneur and O. Lozano 61 Asymmetric Fluorocyclization Reactions 400 V. Gouverneur and O. Lozano 62 Preparation of Allylic Fluorides 405 V. Gouverneur and O. Lozano 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 412 Orlin Petrov, Matthias Schneider, Rolf Bohlmann, Stephan Vettel, and Helmut Vorbr¨uggen 64 Preparation of Rare Earth Fluorosulfides and Oxyfluorosulfides 415 A. Demourgues and A. Tressaud 65 Preparation of Carbon-Fluorine Compounds and Fluoride or Oxide Fluoride-Intercalated Graphites 425 Tsuyoshi Nakajima 66 Safe Synthesis of Superstoichiometric Mesoporous Fluorocarbons 433 Valentin N. Mitkin 67 Preparation of Fluorinated alpha-Alumina 442 Erhard Kemnitz, Toma¡z Skapin, and John M. Winfield 68 High-Yield Synthesis of a Single Asymmetric Isomer of C70(CF3)10 by High-Temperature Radical Trifluoromethylation 447 Natalia B. Shustova, Steven H. Strauss, and Olga V. Boltalina Index 451

About the Author :
HERBERT W. ROESKY, PhD, is Professor Emeritus of Chemistry at the University of Göttingen and past president of the Academy of Sciences of Göttingen. He is a recipient of the ACS Award for Creative Work in Fluorine Chemistry and the H. Moissan Award in Fluorine Chemistry.

Review :
“As Prof. K. Barry Sharpless comments in the Foreword, ‘Many years of experience, together with deep and catholic knowledge of chemical reactivity principles, is the important coin in this [fluorine chemistry] realm’, and I would recommend this book to anyone involved in synthetic chemistry interested in laboratory synthesis involving fluorinating reagents or fluorinated molecules as an introduction into the experimental and chemical reactivity possibilities now available.”  (ChemMedChem, 1 August 2013)