UID:
edoccha_9960161378602883
Format:
1 online resource (792 pages) :
,
illustrations.
ISBN:
0-12-803790-3
Series Statement:
Progress in Fluorine Science Series ; Volume 3
Note:
Front Cover -- Modern Synthesis Processes and Reactivity of Fluorinated Compounds -- Progress in Fluorine Science Series -- Modern Synthesis Processes and Reactivity of Fluorinated Compounds: Progress in Fluorine Science Series -- Copyright -- Contents -- List of Contributors -- Foreword -- 1 - The Cosmic Origin of Fluorine: An Astronomer's View on Fluorine Synthesis -- 1. The Cosmic Origin of the Elements -- 2. The Cosmic Origin of Fluorine -- 2.1 Theoretical Ideas -- 2.2 Observations -- 2.3 What the Future Holds -- References -- 2 - The Fluorine Atom in Health Care and Agrochemical Applications: A Contribution to Life Science -- 1. Introduction -- 1.1 The History of Fluorine in Pharmaceutical Applications -- 1.2 The History of Fluorine in Agrochemical Applications -- 2. Methods to Introduce Fluorine Into Organic Molecules -- 2.1 Fluorinating Agents -- 2.2 Use of Anhydrous HF -- 2.3 Indirect Fluorination: Use of a Building Block Containing a Fluorinated Group -- 3. Use of Trifluoromethyl Group in Pharmaceuticals and Agrochemistry -- 3.1 Synthesis of Trifluoroacetyl Chloride and Trifluoroacetic Acid -- 3.2 Some Active Agrochemical Ingredients Based on Aliphatic Trifluoromethylated Building Blocks -- 3.3 Some Active Pharmaceutical Ingredients Based on Aliphatic Trifluoromethylated Building Blocks -- 4. Use of Difluoromethyl Group in Pharmaceuticals and Agrochemistry -- 4.1 Synthesis Strategy to Obtain CF2 Groups in Active Ingredients -- 4.2 Examples of Active Ingredients Containing the CF2 Group -- 4.3 Use of Difluoromethanesulfonyl Chloride -- References -- 3 - Industrial Syntheses of Hydrohaloolefins and Related Products -- 1. Introduction -- 2. Hydrofluoroolefins -- 2.1 CHFCF2, 1,1,2-Trifluoroethylene or HFO-1123 -- 2.2 E,Z-CF3CHHF, 1,3,3,3-Tetrafluoropropene or HFO-1234ze -- 2.3 CF3CFCH2, 2,3,3,3-Tetrafluoro-1-propene or HFO-1234yf.
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2.3.1 Hexafluoropropene Route -- 2.3.2 Tetrafluoroethylene (CF2CF2) Routes -- 2.3.3 Tetrafluoroethylene-Chloroform Route -- 2.3.4 1230xa (CCl2CClCH2Cl) Route -- 2.3.5 240db (CCl3CClHCH2Cl) Route -- 2.3.6 1243zf (CF3CHCH2) Route -- 2.3.7 114a (CF2ClCF2Cl) and Formaldehyde Route -- 2.3.8 Thermal Pyrolysis Processes -- 2.4 CF3CFCHF, 1,2,3,3,3-Pentafluoro-1-propene or HFO-1225ye -- 2.4.1 Hexafluoropropene Route -- 2.4.2 Tetrafluoroethylene Routes -- 2.4.3 Tetrafluoroethylene-CFC-12 (CCl2F2) Route -- 2.5 CF3CHCH2, 3,3,3-Trifluoropropene or HFO-1243zf -- 2.6 Z-CF3CHCHCF3, 1,1,1,4,4,4-Hexafluoro-2-butene, Z-1336mzz -- 2.7 E-CF3CHCHCF3, (E)-1,1,1,4,4,4-Hexafluorobut-2-ene, E-1336mzz -- 3. Other Hydrofluoroolefins -- 4. Hydrochlorofluoroolefins -- 4.1 E-CF3CHCHCl, E-3,3,3-Trifluoro-1-chloropropene, E-1233zd -- 4.2 Z-CF3CHCHCl, E-3,3,3-Trifluoro-1-chloropropene, E-1233zd -- 4.3 CF3CClCH2, 3,3,3-Trifluoro-2-chloro-1-propene, HFCO-1233xf -- 4.3.1 1230xa (CCl2CClCH2Cl) Route -- 4.3.2 2,3,3,3-Tetrachloropropene (CCl3CClCH2) 1230xf Route -- 4.3.3 240db 1,1,1,2,3-Pentachloropropane Route -- 4.3.4 3,3,3-Trifluoropropene (CF3CHCH2) 1243zf Route -- 4.4 CF3CFCl2, 2,3,3,3-Tetrachloro-1,1-dichloro-1-propene, HCFO-1214ya -- 4.4.1 TFE-HCFC-21 (CHCl2F) Route -- 4.4.2 Other Synthetic Routes to 1214ya -- 5. Conclusion -- References -- 4 - Electrochemical Fluorination: A Powerful Tool for the Preparation of Organofluorine Compounds -- 1. Introduction and Historical Overview -- 2. Technical Aspects of the Electrochemical Fluorination (Simons Process) -- 2.1 Cell Construction and General Requirements for the Electrochemical Fluorination Process -- 2.2 Requirements for Starting Materials for the Electrochemical Fluorination (Simons) Process -- 2.3 Practical Recommendation for the Fluorination of Organic Compounds by the Electrochemical Fluorination Process.
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3. Mechanism of Electrochemical Fluorination (Simons Process) -- 4. Carbon Chain Isomerization During Electrochemical Fluorination (Simons Process) -- 5. Electrochemical Fluorination of the Elementorganic Compounds -- 5.1 Electrochemical Fluorination of the Compounds With CS Bond and Follow-Up Chemistry -- 5.2 Electrochemical Fluorination of the Compounds with SN Bond and Follow-Up Chemistry -- 5.3 Electrochemical Fluorination of the Compounds With CP Bond and Follow-Up Chemistry -- Acknowledgments -- References -- 5 - Once Upon a Time Was the Langlois' Reagent: a "Sleeping Beauty" -- 1. Introduction -- 2. Origin of the Trifluoromethanesulfinate Salts and Their First Uses -- 3. Rebirth of the "Langlois' Reagent" -- 4. Conclusions -- Acknowledgments -- References -- 6 - Toward CF3S Group: From Trifluoromethylation of Sulfides to Direct Trifluoromethylthiolation -- 1. Introduction -- 2. Indirect Methods -- 2.1 Preparation Involving Halogen Exchange Reaction -- 2.2 Trifluoromethylation of Sulfur Compounds -- 2.2.1 Trifluoromethylation of Thiols or Disulfides Involving Radical or SET Mechanisms -- 2.2.1.1 Trifluoroiodomethane as Trifluoromethylating Reagent -- 2.2.1.2 Bromotrifluoromethane as Trifluoromethylating Reagent -- 2.2.1.3 Miscellaneous Trifluoromethylating Reagent -- 2.2.2 Nucleophilic Trifluoromethylation -- 2.2.2.1 Bromotrifluoromethane and Trifluoroiodomethane as Trifluoromethylating Reagents -- 2.2.2.2 Trifluoromethyltrimethylsilane (Ruppert-Prakash Reagent) -- 2.2.2.3 Fluoroform and Fluoral Hemiaminals -- 2.2.2.4 Trifluoromethanesulfinamides and Trifluoromethylsulfones -- 2.2.2.5 Miscellaneous Reagents -- 2.2.3 Electrophilic Trifluoromethylation -- 2.2.3.1 Aryl Trifluoromethyl Sulfonium Salts (Umemoto's Reagents) -- 2.2.3.2 Hypervalent Trifluoromethyl-Iodine(III) Reagents (Togni's Reagents).
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3. Direct Preparation: Trifluoromethylthiolation -- 3.1 Nucleophilic Trifluoromethylthiolation -- 3.1.1 Trifluoromethylthiosilver(I) -- 3.1.2 Trifluoromethylthiocopper(I) -- 3.1.3 Ammonium or Cesium Trifluoromethylthiolate -- 3.1.4 Difluorothiophosgene -- 3.1.5 CF3− Anion/Elemental Sulfur -- 3.1.6 Bis(trifluoromethyl)disulfide and O-Octadecyl-S-trifluorothiolcarbonate -- 3.1.7 From an Electrophilic Reagent: Umpolung Reactivity of Trifluoromethanesulfenamides -- 3.2 Electrophilic Trifluoromethylthiolation -- 3.2.1 Trifluoromethanesulfenyl Chloride and bis-Trifluoromethyl Disulfide -- 3.2.2 Trifluoromethanesulfenamides (Billard's Reagents) -- 3.2.3 N-Trifluoromethylthiophtalimide (Munavalli's Reagent) and N-Trifluoromethylsuccinimide -- 3.2.4 Trifluoromethylsulfenates (Shen's Reagent) -- 3.2.5 N-Trifluoromethylthiosaccharin (Shen's Reagent) -- 3.2.6 Trifluoromethanesulfonyl Hypervalent Iodonium Ylide (Shibata's Reagent) -- 3.2.7 From CF3SAg -- 3.3 Radical Trifluoromethylthiolation -- 3.3.1 Historical Reagents: Trifluoromethanethiol and Trifluoromethanesulfenyl Chloride -- 3.3.2 Trifluoromethylthiosilver(I) -- 3.3.3 Electrophilic Reagents in Radical Pathways -- 4. Conclusions -- References -- 7 - Nucleophilic Di- and Trifluoromethylation of CO and CN Bonds -- 1. Introduction -- 2. Trifluoromethylation Reactions -- 2.1 Silicon Reagents -- 2.2 Derivatives of Trifluoroacetic Acid and Trifluoroacetaldehyde -- 2.3 Miscellaneous Reagents -- 3. Difluoromethylation Reactions -- 3.1 Silicon Reagents -- 3.2 Miscellaneous Reagents -- 4. Conclusion -- Acknowledgments -- References -- 8 - Oxidative Trifluoromethylation and Trifluoromethylthiolation -- 1. Introduction -- 2. Oxidative Trifluoromethylation -- 2.1 Oxidative Trifluoromethylation for the Formation of C(sp)CF3 Bond -- 2.2 Oxidative Trifluoromethylation for the Formation of C(sp2)CF3 Bond.
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2.3 Oxidative Trifluoromethylation for the Formation of C(sp3)CF3 Bond -- 2.4 Oxidative Trifluoromethylation for the Formation of X(P, O, N)CF3 Bond -- 3. Oxidative Trifluoromethylthiolation -- 4. Other Oxidative Fluoroalkylations -- 5. Conclusion -- References -- 9 - Catalytic Enantioselective Fluorination -- 1. Introduction -- 2. Electrophilic Fluorination Methods -- 2.1 Fluorination of Metal Enolates -- 2.2 Tertiary Amine Catalysis -- 2.3 Enamine Catalysis -- 2.3.1 Linear Aldehydes -- 2.3.2 Branched Aldehydes -- 2.3.3 Ketones -- 2.3.4 Other Substrates -- 2.4 Miscellaneous Organocatalysis Catalysts -- 2.5 Chiral Anion Phase Transfer Catalysis -- 2.6 Metal-Catalyzed Fluorinations Not Involving Enolates -- 3. Nucleophilic Fluorination -- 3.1 Ring Opening of Strained Heterocycles -- 3.2 Metal-Catalyzed Allylic Substitution -- 4. Conclusions and Outlook -- References -- 10 - Development of Electrophilic Trifluoromethylating Reagents -- 1. Introduction -- 2. Historical Background -- 3. Electrophilic Trifluoromethylating Reagents -- 3.1 Sulfonium, Selenonium, and Telluronium Salts -- 3.2 Oxonium Salts -- 3.3 Iodine(III) Compounds -- 4. Conclusion85 -- References -- 11 - New Nucleophilic Fluoroalkylations -- 1. Introduction -- 2. Nucleophilic Trifluoroalkylation Reactions -- 2.1 Nucleophilic Metal-Free Trifluoromethylation Reactions -- 2.1.1 (Trifluoromethyl)Trimethylsilane as a Nucleophilic Trifluoromethyl Source -- 2.1.2 CF3H as a Trifluoromethyl Source -- 2.1.3 Sulfur-Derived Trifluoromethylating Reagents -- 2.1.4 Trifluoromethylations Using Phosphonate-, Hexafluoroacetone-, Trifluoroacetaldehyde, and Zinc-Based Reagents -- 2.2 Metal-Assisted Nucleophilic Trifluoromethylation Reactions -- 2.2.1 Copper-Mediated Trifluoromethylations -- 2.2.2 Palladium-Catalyzed Trifluoromethylations -- 2.2.3 Silver-Mediated Trifluoromethylations.
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2.3 Other Perfluoroalkylation Reactions.
Additional Edition:
ISBN 0-12-803740-7
Language:
English
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