Diazo Compounds

Diazo Compounds: Properties and Synthesis focuses on the properties and syntheses of aliphatic diazo compounds. This monograph explores the application of diazo compounds in organic synthesis. Organized into two parts encompassing 16 chapters, this book starts with an overview of the structurally inherent effects of diazoalkenes. This monograph then examines the most important contribution of diazo compounds to the chemistry of carbenes and cycloadditions. Other chapters deal with structure, thermal behavior, acidic decomposition, spectroscopic properties, photochemistry of diazoalkenes, and synthetic methods. This book further discusses the qualitative and quantitative studies of the thermal stabilities of alkyl and aryl diazomethanes. The final chapter deals with the isotope-labeled diazo compounds that are of great importance for investigations of organic reaction mechanisms. This book is intended for chemists with an interest in the synthetic application of diazo compounds. Students and researchers engaged in the study of the physical properties of diazo compounds will find this book extremely useful.

Preface

Part I Properties of Aliphatic Diazo Compounds

Chapter 1 Structure and Spectroscopic Properties

1.1 The Constitution of Diazoalkanes

1.2 Structure and Bonding of Diazoalkanes

1.3 Cis-Trans Isomerism of the α-Diazocarbonyl Compounds

1.4 Metal Complexes with Diazo Compounds as Ligands

1.5 Spectroscopic Properties of Diazoalkanes

References

Chapter 2 Thermal Properties

2.1 Introduction

2.2 Alkyl and Aryl Diazomethanes

2.3 α-Diazocarbonyl Compounds

2.4 α-Diazophosphoryl Compounds

References

Chapter 3 Reactivity toward Acids

3.1 The Acid-Stability of Diazoalkanes

3.2 C- and N-Protonation

3.3 Kinetics and Mechanism of the Reactions with Acids

3.4 Influence of Solvent on Kinetics and Product Distribution

3.5 Products of the Acid-Catalyzed Decomposition

3.6 Diazocarbonyl Compounds and Lewis Acids

References

Chapter 4 Photochemistry of Aliphatic Diazo Compounds

4.1 Introduction

4.2 Diazoalkane-Diazirine Isomerization

4.3 Generation of Carbenes from Diazo Compounds

4.4 Wolff Rearrangement

References

Part II Syntheses of Aliphatic Diazo Compounds

Chapter 5 Diazotization of Amines

5.1 Introduction

5.2 Diazoalkanes

5.3 Fluoro- and Cyanodiazoalkanes

5.4 Diazocarbonyl Compounds

5.5 α-Diazophosphoryl Compounds

5.6 Diazoazoles

References

Chapter 6 The Forster Reaction

6.1 Introduction

6.2 Diazomethane and Aryldiazomethanes

6.3 α-Diazoketones and Sulfones

References

Chapter 7 Introduction of the Diazo Group by Nitrosation

7.1 Introduction

7.2 Diazoazoles

7.3 Diazocarbonyl Compounds

References

Chapter 8 Dehydrogenation of Hydrazones

8.1 Introduction

8.2 Mercury(II) Oxide

8.3 Silver Oxide

8.4 Manganese(IV) Oxide

8.5 Lead(IV) Acetate

8.6 Iodine

8.7 Miscellaneous

References

Chapter 9 The Bamford-Stevens Reaction

9.1 Introduction

9.2 Aryl- and Alkyldiazoalkanes

9.3 Metallated Diazoalkanes

9.4 α, β-Unsaturated Diazoalkanes

9.5 α-Diazocarbonyl Compounds

9.6 α-Diazophosphoryl Compounds

References

Chapter 10 Alkaline Cleavage of β-(Ν-Alkyl-N-nitrosoamino)ketones and -sulfones

10.1 Introduction

References

Chapter 11 Alkaline Cleavage of (N-Alkyl-N-nitroso-aminomethyl)carboxamides and -urethanes

References

Chapter 12 Acyl Cleavage of N-Alkyl-N-nitrosoacidamides

12.1 Introduction

12.2 Mechanism of Cleavage

12.3 N-Alkyl-N-nitrosourethanes

12.4 N-Alkyl-N-nitrosoureas

12.5 N-Alkyl-N'-nitro-N-nitrosoguanidines

12.6 N-Alkyl-N-nitrosocarboxamides

12.7 N-Alkyl-N-nitroso-p-toluenesulfonamides

References

Chapter 13 Diazo Group Transfer

13.1 Introduction

13.2 To Active Methylene Compounds

13.3 To α-Acylcarbonyl Compounds

13.4 Diazo Group Transfer to Alkenes

13.5 Diazo Group Transfer to Acceptor-Substituted Methylene Triphenylphosphoranes and Triphenylphosphonium Salts

13.6 Diazo Group Transfer to Alkynes

References

Chapter 14 Substitution Reactions of Diazoalkanes

14.1 Introduction

14.2 Metallation

14.3 Transmetallation Reactions

14.4 Halogenation

14.5 Nitration

14.6 C-Alkylation

14.7 C-Acylation

14.8 Acyl Cleavage

14.9 Miscellaneous Reactions

References

Chapter 15 Miscellaneous Methods

15.1 Ring Cleavage of Heterocycles

15.2 Condensation Reactions

15.3 Cleavage Reactions

15.4 Fragmentation of Heterocyclic Compounds

References

Chapter 16 Isotope-Labeled Diazo Compounds

16.1 Introduction

16.2 Diazomethanes

16.3 α-Diazocarbonyl Compounds

References

Bibliography

Addendum

Index