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.
Inhalt
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 a-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 a-Diazocarbonyl Compounds
2.4 a-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 a-Diazophosphoryl Compounds
5.6 Diazoazoles
References
Chapter 6 The Forster Reaction
6.1 Introduction
6.2 Diazomethane and Aryldiazomethanes
6.3 a-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 a, ß-Unsaturated Diazoalkanes
9.5 a-Diazocarbonyl Compounds
9.6 a-Diazophosphoryl Compounds
References
Chapter 10 Alkaline Cleavage of ß-( -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 a-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 a-Diazocarbonyl Compounds
References
Bibliography
Addendum
Index