Synthesis and Reactions of α-Haloalkyl Isocyanates

A review of the methods of preparation of α-haloalkyl isocyanates is given and their chemical transformations are discussed. 1. Introduction 2. Synthesis of α-Haloalkyl Isocyanates 2.1. Curtius and Hofmann Reactions 2.2. Reactions of Imino Compounds with Phosgene and Analogues 2.3. Reactions of Nitriles with Phosgene and Fluorophosgene 2.4. Halogenation of Alkyl Isocyanates 2.5. Fluorination of α-Chloroalkyl Isocyanates 2.6 Reactions of α-Hydroxyalkyl Isocyanates, N-(α-Hydroxyal-kyl)- urethanes, and Derivatives with Chlorinating Agents 2.7. Reactions of Acyl and Thioacyl Isocyanates with Chlorinating Agents 2.8. Introduction of the Isocyanate Group by Exchange Reactions 2.9. Addition of Halogen to α-Alkenyl Isocyanates and Aryl Isocyanates 2.10. Preparation from N-(α-Haloalkyl)-carbonimidic Dichlorides 2.11. Specific Methods for the Synthesis of α-Fluoroalkyl Isocyanates 3. Reactions of α-Haloalkyl Isocyanates 3.1. Tautomerism of α-Haloalkyl Isocyanates 3.2. Reactions with Nucleophiles Containing Mobile Hydrogen Atoms 3.3. Exchange Reactions with N-Silylated Heterocumulenes 3.4. Elimination of Hydrogen Halides and Halogens 3.5. Addition to Multiple Bond Systems 3.6. Reactions with Oxiranes and N-Substituted Aziridines 3.7. Friedel-Crafts Reactions 3.8. Reactions with Alkylidenephosphoranes and Iminophosphoranes 3.9. Arbuzov Reaction 3.10. Reactions with Tertiary Amines and Tertiary Phosphines 3.11. Other Reactions