Diazo Compounds: Properties and Synthesis

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.

Table of Contents:
PrefacePart 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 ReferencesPart 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 ReferencesBibliographyAddendumIndex