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.

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

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.