The Chemistry of Imidoyl Halides, 1968

Primarily, the aim of this book is to provide a reference work for senior students and research workers engaged in the synthetic aspects of chemistry. The various classes of compounds under discussion provide useful interme­ diates for the synthesis of numerous nitrogen-containing derivatives. Imidoyl halides are also intermediates in several classical name reactions, such as the Gattermann, Houben-Hoesch, and Vilsmeier-Haack syntheses of aldehydes and ketones, the Beckmann rearrangement, and the v. Braun degradation. Some imidoyl halides have shown interesting agricultural activities, and the generation of highly reactive species (ketenimines, nitrile oxides, nitrile imides, carbodiimides, etc.) from imidoyl halides has contributed to the study of polar cycloaddition reactions. To enable researchers to utilize this chemistry without consulting the original references, I have included a number of selected working examples. This procedure will facilitate the transformation of written information into well designed experiments, especially since part of the cited literature is not readily available. The book is organized around classes of imidoyl halides, with synthesis and chemistry discussed in an orderly fashion. The physical properties of the known imidoyl halides are listed in tables, and I have attempted to draw attention to the more recent literature. The one or two references provided for each compound represent those which best describe its physical constants and synthesis.

1. Introduction.- I. Scope.- II. Reactivity.- III. General Reactions.- IV. Physicochemical Data.- V. References.- 2. Carbonimidoyl Dihalides.- I. Introduction.- II. Synthesis.- A. Addition of Halogen to Isocyanides.- B. Halogenation of Isothiocyanates.- C. Halogenation of Isocyanates and Carbamoyl Halides.- D. Halogenation of Imidoyl Chlorides.- E. Halogenation of Amines.- F. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reaction with Oxygen-Hydrogen Bonds.- B. Reaction with Sulfur-Hydrogen Bonds.- C. Reaction with Nitrogen-Hydrogen Bonds.- D. Addition to the C=N Bond.- E. Miscellaneous Reactions.- V. References.- 3. Imidoyl Halides.- I. Introduction.- II. Synthesis.- A. Halogenation of Thioamides.- B. Halogenation of Amides.- C. Addition of Hydrogen Halides to Nitriles and Isonitriles.- D. From other C=N Double Bond Compounds.- E. Halogenation of Amines, Imines and Carbamoyl Chlorides.- F. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reaction with Oxygen-Hydrogen Bonds.- B. Reaction with Sulfur-Hydrogen Bonds.- C. Reaction with Nitrogen-Hydrogen Bonds.- D. Reaction with Carbon-Hydrogen Bonds.- E. Addition and Elimination Reactions.- F. Miscellaneous Reactions.- V. References.- 4. Haloformamidines.- I. Introduction.- II. Synthesis.- A. Halogenation of Thioureas.- B. Halogenation of Ureas.- C. Addition of Halides to Cyanamides and Carbodiimides.- D. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reactions with Oxygen-Hydrogen Bonds.- B. Reactions with Sulfur-Hydrogen Bonds.- C. Reactions with Nitrogen-Hydrogen Bonds.- D. Addition and Elimination Reactions.- V. References.- 5. 1-Haloformimidates and 1-Halothioformimidates.- I. Introduction.- II. Synthesis.- A. From Carbamates and Thiocarbamates.- B. From Carbonimidoyl Dihalides.- C. From Isocyanides.- D. From Thiocyanates and Isothiocyanates.- E. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reactions with Oxygen-Hydrogen Bonds.- B. Reactions with Nitrogen-Hydrogen Bonds.- C. Reactions with Carbon-Hydrogen Bonds.- D. Addition and Elimination Reactions.- V. References.- 6. Hydroxamoyl Halides.- I. Introduction.- II. Synthesis.- A. Halogenation of Aldoximes.- B. From Nitrile Oxides.- C. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reaction with Oxygen-Hydrogen Bonds.- B. Reaction with Sulfur-Hydrogen Bonds.- C. Reaction with Nitrogen-Hydrogen Bonds.- D. Reaction with Carbon-Hydrogen Bonds.- E. Addition and Elimination Reactions.- F. Miscellaneous Reactions.- V. References.- 7. Hydrazidoyl Halides.- I. Introduction.- II. Synthesis.- A. From Carboxylic Acid Hydrazides and Phosphorous Halides.- B. From Diazonium Halides.- C. Halogenation of Hydrazones.- D. Halogenation of Azo Compounds and Azines.- E. Miscellaneous Methods.- III. Physicochemical Properties.- IV. Chemical Behavior.- A. Reaction with Oxygen-Hydrogen Bonds.- B. Reaction with Sulfur-Hydrogen Bonds.- C. Reactions with Nitrogen-Hydrogen Bonds.- D. Reactions with Carbon-Hydrogen Bonds.- E. Addition and Elimination Reactions.- F. Miscellaneous Reactions.- V. References.- 8. Cyclic Imidoyl Halides.- I. Introduction.- II. Three-Membered Ring Imidoyl Halides.- III. Five-Membered Ring Imidoyl Halides.- IV. Six-Membered Ring Imidoyl Halides.- V. Seven-Membered Ring Imidoyl Halides.- VI. References.