Efficient Preparations of Fluorine Compounds

The definitive guide to creating fluorine–basedcompounds and the materials of tomorrow

Discovered as an element by the French chemist Henri Moissan in1886, through electrolysis of potassium fluoride in anhydroushydrogen fluoride "le fluor," or fluorine, began its chemicalhistory as a substance both elusive and dangerous. With a slightpale yellow hue, fluorine is at room temperature a poisonousdiatomic gas. Resembling a spirit from a chemical netherworld,fluorine is highly reactive, difficult to handle, yet veryversatile as a reagent with the power to form compounds withalmost any other element.

Comprising 20% of pharmaceutical products and 30% ofagrochemical compounds, as well as playing a key role in electriccars, electronic devices, and space technology, compoundscontaining fluorine have grown in importance across the globe.Learning how to safely handle fluorine in the preparation ofinnovative new materials with valuable newproperties is of critical importance to chemists today.Bringing together the research and methods of leading scientists inthe fluorine field, Efficient Preparations of FluorineCompounds is the definitive manual to creating, andunderstanding the reaction mechanisms integral to a wide variety offluorine compounds. With sixty–eight contributed chapters, thebook′s extensive coverage includes:

Preparation of Elemental Fluorine Synthesis Methods for Exotic Inorganic Fluorides with VariedApplications Introduction of Fluorine into Compounds via Electrophilic andNucleophilic Reactions Direct Fluorination of Organic Compounds with ElementalFluorine Efficient Preparations of Bioorganic Fluorine Compounds Asymmetric Fluorocyclization Reactions Preparations of Rare Earth Fluorosulfides andOxyfluorosulfides

The book offers methods and results that can be reproduced bystudents involved in advanced studies, as well as practicingchemists, pharmaceutical scientists, biologists, and environmentalresearchers. The only chemical resource of its kind, EfficientPreparations of Fluorine Compounds from its firstexperiment to its last is a unique window into the centuriesold science of fluorine and the limitless universe offluorine–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 Acetonitrile16
Dmitry V. Peryshkov, Eric V. Bukovsky, and Steven H.Strauss

6 Efficient Preparation of the Highly Soluble ortho– andpara–C60(CF2C6F5)2 Derivatives 19
Igor V. Kuvychko, Bryon W. Larson, Steven H. Strauss, and OlgaV. Boltalina

7 Synthesis of Cs[1–H–CB11F11] 22
Michal Vala¡sek, Filip embera, Michael J. Hughes,Ivan Stibor, Zbyn¡ek Janou¡sek, and Josef Michl

8 Synthesis of Zero–Valent Trifluoromethyl ChalcogenatoDerivatives, [NMe4]ECF3 (E = S, Se, Te), and Related Compounds26
Wieland Tyrra and Silke Kremer

9 Synthesis Methods for Exotic Inorganic Fluorides with VariedApplications 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 CoordinatingTetrakis(pentafluorophenyl)borate Anion, [B(C6F5)4] 60
Hermann–Josef Frohn

11 Pentafluorophenyldifluoroborane, C6F5BF2, andPentafluorophenyltrifluorosilane, C6F5SiF3, Versatile Reagents forFluorine/Pentafluorophenyl Substitution Reactions in StronglyOxidizing Hypervalent Nonmetal Fluorides 65
Hermann–Josef Frohn

12 Iodine(III and V) Fluorides: Interesting Fluorinating Agents72
Hermann–Josef Frohn

13 Tetramethylammonium Fluoride, [N(CH3)4]F, a Widely ApplicableReagent to Introduce Fluoride Ions and a Suitable Nucleophile toInitiate the Transfer of Perfluoroorganyl Groups to Electrophiles76
Hermann–Josef Frohn

14 Preparation of Transition Metal Sulfide Fluorides 79
Michael Gerken

15 Transition Metal Carbonyl Sulfur Dioxide and ThiazylfluorideComplexes: Reactions at the Metal Center and at the Ligand 82
Rudiger Mews

16 Cesium, Mercury, and Silver Salts withSulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSFBuilding Blocks 88
Rudiger Mews

17 Laboratory–Scale Synthesis of Gold Trifluoride and UraniumHexafluoride 94
Thomas M. Klapotke

18 Preparation of Transition Metal Fluorides using ClF3100
Ralf Haiges

19 Preparation of Fluorine–Containing Molecular Halides andHeteropolar Salts with Elements of Group 15 and Niobium andTantalum Halides 108
Lothar Kolditz

20 Fluoro and Fluorohydroxy Complexes of As, Sb, and Sn117
Lothar Kolditz

21 Trifluoromethyl Compounds via Electrophilic and NucleophilicReactions 121
Jeanne M. Shreeve

22 Introduction of Fluorine into Compounds via Electrophilic andNucleophilic Reactions 127
Jeanne M. Shreeve

23 The "Real" Iodine and Bromine Monofluorides 133
Shlomo Rozen

24 The Versatile Chemistry of Acetyl Hypofluorite: The FirstHypofluorite Not Bonded to a Polyhaloalkyl Group 139
Shlomo Rozen

25 Direct Fluorination of Organic Compounds with ElementalFluorine 146
Shlomo Rozen

26 The Surprising Chemistry of Bromine Trifluoride 154
Shlomo Rozen

27 Preparation of Silicon– and Sulfur–Based Fluorinated MethaneDerivatives as Versatile Fluoromethylation Reagents 173
G.K. Surya Prakash and Fang Wang

28 Pentafluoroethyl Lithium: Reactions with Carbonyl Compoundsand 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–SubstitutedAcetylenes for Liquid Crystals 214
Olesya Kazakova, Maxim Ponomarenko, and Gerd–VolkerRoschenthaler

31 Delocalized Lipophilic Cations as a Source of Naked Fluorideand Phase–Transfer Catalysts 220
Nataliya Kalinovich, Olesya Kazakova, and Gerd–VolkerRoschenthaler

32 Methyltrifluoropyruvate Imines Possessing N–oxalyl andN–Phosphonoformyl Groups: Precursors to a Variety ofAlpha–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–boronateEster 235
Michael Teltewskoi and Thomas Braun

35 Palladium–Mediated Synthesis of 4–Vinyltetrafluoropyridineand 2,3,5,6–Tetrafluoropyridine 237
David Breyer and Thomas Braun

36 Preparation of Polyfluoroaryl–1,2–difluorovinylsilanes240
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)benzene246
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–trifluoropropanal250
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 UnsymmetricalBis((perfluoroalkyl)sulfonyl)imide 256
Darryl D. Desmarteau and Thomas D. Hickman

43 Preparation of Perfluoroalkyl Sulfilimines and Sulfoximines262
Emmanuel Magnier

44 Preparation of Trifluoromethylsulfonium Salts 266
Emmanuel Magnier

45 Preparation of Organometallic Fluorides of Main Group andTransition Elements 270
Herbert W. Roesky

46 Preparation of Pentafluorosulfanyl Carbonyl Compounds275
John T. Welch

47 Preparation of Power–Variable ElectrophilicTrifluoromethylating Agents, S–(Trifluoromethyl)dibenzothiopheniumSalts Series 279
Teruo Umemoto

48 Synthesis of Fluorine–Containing Heterocycles fromalpha,alpha–Dihydropolyfluoroalkylsulfides and FluorinatedThiocarboxylic 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, EvanD. 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 andOxofluorocomplex Anions by Fluoroacid Base Reactions334
Kazuhiko Matsumoto and Rika Hagiwara

52 Synthesis of Difluorocyclopropyl Building Blocks:2,2–Difluorocyclopropylmethanol and2–(Bromomethyl)–1,1–difluorocyclopropane 338
Wei Xu and William R. Dolbier Jr.

53 Preparation of1,1,2,2,9,9,10,10–Octafluoro[2.2]paracyclophane andPerfluoro[2.2]paracyclophane 343
William R. Dolbier Jr., Jian–Xi Duan, Alex J. Roche, and LianhaoZhang

54 Synthesis and Application of gem–Difluoromethylenated andTrifluoromethylated Building Blocks 349
Feng–Ling Qing and Xiao–Long Qiu

55 1,3–Dipolar Cycloaddition Reactions to Fluoroalkenes365
Hanna Wojtowicz–Rajchel and Henryk Koroniak

56 Synthesis of Fluorinated Vinyl Derivatives of Nucleic AcidBases 370
Hanna Wojtowicz–Rajchel, Donata Pluskota–Karwatka, and HenrykKoroniak

57 Synthesis of CF3–Substituted Aziridine Ring by the GabrielReaction 375
Tomasz Cytlak, Bartosz Marciniak, and Henryk Koroniak

58 Preparation of alpha–Fluoro Amino and alpha–Fluoro EnaminoReagents 379
Justyna Walkowiak and Henryk Koroniak

59 Synthesis of Original Fluoromonomers and Their RadicalCopolymerization 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 UsingPerfluoro n–Butylsulfonyl Fluoride (Nonaflyl Fluoride) inCombination 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 andOxyfluorosulfides 415
A. Demourgues and A. Tressaud

65 Preparation of Carbon–Fluorine Compounds and Fluoride orOxide Fluoride–Intercalated Graphites 425
Tsuyoshi Nakajima

66 Safe Synthesis of Superstoichiometric MesoporousFluorocarbons 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 ofC70(CF3)10 by High–Temperature Radical Trifluoromethylation447
Natalia B. Shustova, Steven H. Strauss, and Olga V.Boltalina

Index 451

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

As Prof. K. Barry Sharpless comments in the Foreword, Many years of experience, together with deep and catholicknowledge of chemical reactivity principles, is the important coinin this [fluorine chemistry] realm , and I would recommendthis book to anyone involved in synthetic chemistry interested inlaboratory synthesis involving fluorinating reagents or fluorinatedmolecules as an introduction into the experimental and chemicalreactivity possibilities now available.  (ChemMedChem, 1 August 2013)