Chemistry of Organic Fluorine Compounds II A Critical Review

Milos Hudlicky, Editor Virginia Poiytechnic Institute and State University

Attila E. Pavlath, Editor Agricultural Research Service, U. S. Department of Agriculture

ACS Monograph 187

American Chemical Society Washington, DC 1995

CONTENTS

Preface xiii

How To Use This Book xv

Abbreviations xvii

Procedures xix

Contributors xxi

1 Survey of the Literature of Organic Fluorine Chemistry 1 Milos Hudlicky and Atüla E. Pavlath

2 Survey of Fluorinating Agents 23 Dayal T. Meshri

3 Methods of Introducing Fluorine into Organic Molecules Addition of Fluorine 41

Suzanne T. Purrington

Addition of Hydrogen Fluoride 54 Andrew E. Feiring

Addition of Halogen Fluorides to Unsaturated Systems 61 Andrew E. Feiring

Addition of Fluorine and Other Elements 70 Andrew E. Feiring

Replacement of Hydrogen by Fluorine 97 James L. Adcock

Replacement by Means of High-Valency Fluorides 120 Milos Hudlicky

Electrophilic Fluorination of Carbon-Hydrogen Bonds 133 Timothy B. Patrick

Replacement of Halogens by Fluorine 172 Donald F. Halpern and Gerald G. Vernice

Replacement of Oxygen by Fluorine 199 W. Dmowski

ix

Replacement of Sulfur by Fluorine 263 W. Dmowski

Replacement of Nitrogen by Fluorine 271 MaxM. Boudaklan

4 Reactions of Organic Fluorine Compounds Reduction 297

C. G. Krespan

Oxidation 321 Oldrich Paleta

Halogenation 364 S. R. Elsheimer

Nitration 387 G. L. Cantrell and J. F. Lang

Nitrosation 398 G. L. Cantrell and J. F. Lang

Sulfonation 403 G. L. Cantrell and J. F. Lang

Acid-Catalyzed Syntheses 408 G. L. Cantrell and J. F. Lang

Hydrolysis 422 W. H. Gumprecht

Alkylation 446 C. Wakselman

Fluorocarbene Insertions 497 R. L. Soulen

Arylation 501 Timothy B. Patrick

Acylation 525 R. W. Lang

Fluorinated Sulfur, Phosphorus, Boron, and Silicon Compounds 545 J. T. Welch and Seniz Turner-McMullin

Base-Catalyzed Condensations 615 J. T. Welch

Reactions of Fluoromagnesium and Fluorolithium Compounds 646 C. Tamborski

Other Organometallic Syntheses 670 Donald J. Burton andZhen-Yu Yang

Additions: Linear Additions across Double Bonds 729 L. G. Sprague, K. B. Baucom, S. F. Seilers, and R. A. DuBoisson

x

Linear Additions to Acetylenic Compounds 757 R, L. Soulen

Cycloadditions Forming Three- and Four-Membered Rings 767 B. E. Smart

Cycloadditions Forming Five- and Six-Membered Rings 797 W. R. Dolbier

Addition Reactions across Polyfluoroalkyl- and Perfluoroalkyl-Substituted CO and CN Multiple Bond Systems 840

K. Burger, N. Sewald, C. Schierlinger, and E. Brunner

Eliminations 888 M. Hudlicky and A. E. Pavlath

Molecular Rearrangements and Pyrolysis 913 H. Koroniak

5 Fluorinated Compounds as Reagents 939 Peter J. Stang and Viktor V. Zhdankin

6 Properties of Fluorinated Compounds Physical and Physicochemical Properties 979

B. E. Smart

Biological Properties 1011 R. Filier and K. Kirk

7 Analysis of Organic Fluorine Compounds Destructive Analytical Methods 1023

Dayal T. Meshri

Modern Methods of Separation, Identification, and Structure Determination 1029

Mark L. Robin

Nuclear Magnetic Resonance Spectroscopy of Organofluorine Compounds 1037

T. Stephen Everett

8 Applications of Fluorinated Compounds Refrigerants, Propellants, and Foam-Blowing Agents 1089

R. L. Powell

Fire Suppression Agents 1099 Mark L. Robin

Organic Fluoropolymers 1101 W. W. Schmiegel

XI

Fluorinated Pharmaceuticals 1119 Arthur J. Elliott

18F-Labeled Radiopharmaceuticals 1126 D. F. Holpern

Fluorinated Anesthetics 1133 L. L. Fer standig

Perfluorinated Liquids in Biology and Medicine 1138 L. C. Clark

Fluorinated Agrochemicals 1143 R. W. Lang

Author Index 1149

Subject Index 1247

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