Nucleophile Substitutionen an Kohlensäurederivaten. XX. Aminolyse des Bis(trichlormethyl)carbonates

• Published in: Journal für Praktische Chemie
• Main Authors: Cotarca, Livius, Bacaloglu, R., Csunderlik, C., Marcu, N., Tarnaveanu, A.
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 1987
• Subjects: Carbonic acid
• Online Access: http://dx.doi.org/10.1002/prac.19873290616; http://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fprac.19873290616; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fprac.19873290616; https://onlinelibrary.wiley.com/doi/pdf/10.1002/prac.19873290616

Nucleophilic Substitutions at Carbonic Acid Derivatives. XX. Aminolysis of Bis(trichlormethyl)carbonate The rate constants for the two steps of the reaction of bis(trichlormethyl)carbonate with substituted anilines have been determinated by conductivity measurements. The first relatively fast step of the reaction is the nucleophilic attack of the amine to the bis(trichloromethyl)‐carbonate leading to trichloromethylurethane through a six or four centers transition state in which the carbon‐nitrogen bond is formed parallel with the transfer of the proton. In this reaction a phosgene molecule is also produced, which reacts very fast with amine to form a N,N′‐diarylurea. The second, much slower step, is the nucleophilic attack of the amine to the trichloromethylurethane. Through a similar transition state in which the proton transfer has even a higher importance, a N,N′‐disubstituted urea and an other molecule of phosgene are formed.