Nucleophile Substitutionen an Kohlensäurederivaten. XII. Kinetik und Mechanismus der Reaktion von N-Nitro-N-alkylurethanen mit primären aliphatischen Aminen

✍ Scribed by Dr. R. Bacaloglu; Y. Prodan-Deac; C. Csunderlik; P. Csomos

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 550 KB
• Volume: 322
• Category: Article
• ISSN: 1615-4150
• DOI: 10.1002/prac.19803220103

✦ Synopsis

Nucleophilic Substitutions to Carbonic Acid Derivates. XII. Kinetics and Mechanism of the Reaction of N‐Nitro‐N‐alkyl‐urethanes with Primary Aliphatic Amines

The aminolysis of N‐alkyl‐N‐nitrourethanes takes place, as the kinetical studies demonstrate, by means of several consecutive steps.

The nucleophilic attack of the amine (first step; reaction B), as well as the proton‐transfere (second step; reaction C), are quick pre‐equilibres, followed by the slow, rate‐determining elimination of the nitramino‐group (reaction D).

During the deprotonation, an intermediate with two to the nitramino‐group antiperiplanar orbitals is formed, providing the necessary mesomeric assistance of the elimination.