Efficient Preparations of Fluorine Compounds

Herbert W. Roesky

• Publisher: Wiley
• Year: 2012
• ISBN:
  9781118409442
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Inorganic Chemistry

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

• Cover
• Title Page
• Copyright
• FOREWORD
• PREFACE
• CONTRIBUTORS
• CHAPTER 1: Preparation of Elemental Fluorine
• CHAPTER 2: Preparation of Highly Active Cesium Fluoride
• CHAPTER 3: Preparation of Highly Active Silver Fluoride
• CHAPTER 4: A Room-Temperature Non-Irradiative Synthesis of XeF2
• CHAPTER 5: Efficient Perfluorination of K2B12H12 in Neutral Acetonitrile
• CHAPTER 6: Efficient Preparation of the Highly Soluble ortho- and para-C60(CF2C6F5)2 Derivatives
• CHAPTER 7: Synthesis of Cs[1-H-CB11F11]
• CHAPTER 8: Synthesis of Zero-Valent Trifluoromethyl Chalcogenato Derivatives, [NMe4]ECF3 (E = S, Se, Te), and Related Compounds
• CHAPTER 9: Synthesis Methods for Exotic Inorganic Fluorides with Varied Applications
• CHAPTER 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]−
• CHAPTER 11: Pentafluorophenyldifluoroborane, C6F5BF2, and Pentafluorophenyltrifluorosilane, C6F5SiF3, Versatile Reagents for Fluorine/Pentafluorophenyl Substitution Reactions in Strongly Oxidizing Hypervalent Nonmetal Fluorides
• CHAPTER 12: Iodine(III and V) Fluorides: Interesting Fluorinating Agents
• CHAPTER 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
• CHAPTER 14: Preparation of Transition Metal Sulfide Fluorides
• CHAPTER 15: Transition Metal Carbonyl Sulfur Dioxide and Thiazylfluoride Complexes: Reactions at the Metal Center and at the Ligand
• CHAPTER 16: Cesium, Mercury, and Silver Salts with Sulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks
• CHAPTER 17: Laboratory-Scale Synthesis of Gold Trifluoride and Uranium Hexafluoride
• CHAPTER 18: Preparation of Transition Metal Fluorides using ClF3
• CHAPTER 19: Preparation of Fluorine-Containing Molecular Halides and Heteropolar Salts with Elements of Group 15 and Niobium and Tantalum Halides
• CHAPTER 20: Fluoro and Fluorohydroxy Complexes of As, Sb, and Sn
• CHAPTER 21: Trifluoromethyl Compounds via Electrophilic and Nucleophilic Reactions
• CHAPTER 22: Introduction of Fluorine into Compounds via Electrophilic and Nucleophilic Reactions
• CHAPTER 23: The “Real” Iodine and Bromine Monofluorides
• CHAPTER 24: The Versatile Chemistry of Acetyl Hypofluorite: The First Hypofluorite Not Bonded to a Polyhaloalkyl Group
• CHAPTER 25: Direct Fluorination of Organic Compounds with Elemental Fluorine
• CHAPTER 26: The Surprising Chemistry of Bromine Trifluoride
• CHAPTER 27: Preparation of Silicon- and Sulfur-Based Fluorinated Methane Derivatives as Versatile Fluoromethylation Reagents
• CHAPTER 28: Pentafluoroethyl Lithium: Reactions with Carbonyl Compounds and Epoxides
• CHAPTER 29: Synthesis of γ-Hydroxy-α,α-difluoromethylenephosphonates
• CHAPTER 30: Synthesis of Pentafluoro-λ6-sulfanyl-Substituted Acetylenes for Liquid Crystals
• CHAPTER 31: Delocalized Lipophilic Cations as a Source of Naked Fluoride and Phase-Transfer Catalysts
• CHAPTER 32: Methyltrifluoropyruvate Imines Possessing N-oxalyl and N-Phosphonoformyl Groups: Precursors to a Variety of α-CF3-α-Amino Acid Derivatives
• CHAPTER 33: Rhodium-Mediated Synthesis of (3,3,3- Trifluoropropyl)trimethoxysilane and (3,3,3-Trifluoropropyl)triphenylsilane
• CHAPTER 34: Rhodium-Mediated Synthesis of a Tetrafluoropyridyl-2-boronate Ester
• CHAPTER 35: Palladium-Mediated Synthesis of 4-Vinyltetrafluoropyridine and 2,3,5,6-Tetrafluoropyridine
• CHAPTER 36: Preparation of Polyfluoroaryl-1,2-difluorovinylsilanes
• CHAPTER 37: Preparation of (Z)-2-iodo-1,2-difluorostyrenes
• CHAPTER 38: Preparation of 1,4-Bis(Z-2-iodo-1,2-difluoroethenyl)benzene
• CHAPTER 39: Stereospecific Carboamidation Route to (Z)-N-Phenyl-2,3-difluoro-3-(triethylsilyl) acrylamide
• CHAPTER 40: Preparation of 2-Trifluoromethyl- 3,3,3-trifluoropropanal
• CHAPTER 41: Synthesis of Tetrafluorocatechol
• CHAPTER 42: Preparation of an Unsymmetrical Bis((perfluoroalkyl)sulfonyl)imide
• CHAPTER 43: Preparation of Perfluoroalkyl Sulfilimines and Sulfoximines
• CHAPTER 44: Preparation of Trifluoromethylsulfonium Salts
• CHAPTER 45: Preparation of Organometallic Fluorides of Main Group and Transition Elements
• CHAPTER 46: Preparation of Pentafluorosulfanyl Carbonyl Compounds
• CHAPTER 47: Preparation of Power-Variable Electrophilic Trifluoromethylating Agents, S-(Trifluoromethyl) dibenzothiophenium Salts Series
• CHAPTER 48: Synthesis of Fluorine-Containing Heterocycles from α,α-Dihydropolyfluoroalkylsulfides and Fluorinated Thiocarboxylic Acids Derivatives
• CHAPTER 49: Synthesis of Octafluorocyclooctatetraene
• CHAPTER 50: Preparation of Fluoroolefins
• CHAPTER 51: Preparation of Ionic Liquids of Fluorocomplex and Oxofluorocomplex Anions by Fluoroacid–Base Reactions
• CHAPTER 52: Synthesis of Difluorocyclopropyl Building Blocks: 2,2-Difluorocyclopropylmethanol and 2-(Bromomethyl)-1,1-difluorocyclopropane
• CHAPTER 53: Preparation of 1,1,2,2,9,9,10,10-Octafluoro[2.2]paracyclophane and Perfluoro[2.2]paracyclophane
• CHAPTER 54: Synthesis and Application of gem-Difluoromethylenated and Trifluoromethylated Building Blocks
• CHAPTER 55: 1,3-Dipolar Cycloaddition Reactions to Fluoroalkenes
• CHAPTER 56: Synthesis of Fluorinated Vinyl Derivatives of Nucleic Acid Bases
• CHAPTER 57: Synthesis of CF3-Substituted Aziridine Ring by the Gabriel Reaction
• CHAPTER 58: Preparation of α-Fluoro Amino and α-Fluoro Enamino Reagents
• CHAPTER 59: Synthesis of Original Fluoromonomers and Their Radical Copolymerization with Vinylidene Fluoride
• CHAPTER 60: Convergent 18F Radiosynthesis
• CHAPTER 61: Asymmetric Fluorocyclization Reactions
• CHAPTER 62: Preparation of Allylic Fluorides
• CHAPTER 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
• CHAPTER 64: Preparation of Rare Earth Fluorosulfides and Oxyfluorosulfides
• CHAPTER 65: Preparation of Carbon–Fluorine Compounds and Fluoride or Oxide Fluoride-Intercalated Graphites
• CHAPTER 66: Safe Synthesis of Superstoichiometric Mesoporous Fluorocarbons
• CHAPTER 67: Preparation of Fluorinated γ-Alumina
• CHAPTER 68: High-Yield Synthesis of a Single Asymmetric Isomer of C70(CF3)10 by High-Temperature Radical Trifluoromethylation
• INDEX