Reaktionen der substituierten 1,3,3-Trichloro-2-aza-propene [N-(1,1-Dichloro-alkyl)-imidchloride]

Polychloro-2-azapropenes are readily accessible via high-temperature chlorination of alkyl isocyanide dichlorides, N-alkylimidoyl chlorides, and Schiff bases¹. The present review surveys the synthetically useful reactions of the lowest representative of the series, pentachloro-2-azapropene (trichloromethyl isocyanide dichloride, TMI) and shows that the ring-closure reactions of this compound can also be carried out with the higher homologous 1,3,3-trichloro-2-azapropenes 1. Reactions of Trichloromethyl Isocyanide Dichloride (TMI) involving Cleavage of the Molecule 1.1. Hydrolysis of TMI 1.2. Intramolecular Dehydration by TMI 1.3. Reaction of TMI with Alcohols 1.4. Reaction of TMI with Carboxylic Acids 1.5. Reaction of TMI with Sulfonic Acids 2. Reaction of Trichloromethyl Isocyanide Dichloride (TMI) with Carbonyl Groups 2.1. Conversion of Aldehydes into 1,1-Dichloroalkanes 2.2. Conversion of Carboxylic Acid Anhydrides into the Acid Chlorides 3. Reactions of Trichloromethyl Isocyanide Dichloride (TMI) as a Carbonic Acid Derivative (Synthesis of Orthocarbonates) 3.1. Reaction of TMI with Monofunctional Phenols and Trichloroethanol 3.2. Reaction of TMI with Polyfunctional Phenols 4. Syntheses involving Incorporation of the C-3 Atom of Trichloromethyl Isocyanide Dichloride (TMI) or Substituted 1,3,3-Trichloro-2-azapropenes into N-Heterocyclic Compounds 4.1. Synthesis of 1,3,5-Triazines 4.2. Synthesis of Pyrimidines 4.3. Synthesis of Quinazolines 4.4. Synthesis of 1,2,4-Triazoles 4.5. Synthesis of 1,2,4-Oxadiazoles