Summary
N-Arylsubstituted ureas undergo exchange of the N′-residue upon reaction with amines. Using kinetic measurements, investigation of product distribution, regioselectivity, catalysis, and substrate influences, it was shown that this reaction proceeds via a second order nucleophilic substitution at the urea carbonyl center. By means of semiempirical calculations using the MNDO method the alternative mechanism of fragmentation was investigated.
Zusammenfassung
N-Arylsubstituierte Harnstoffe erleiden bei der Reaktion mit Aminen einen Austausch des N′-Restes. Durch kinetische Messungen, Untersuchung der Produktverteilung, Regioselektivität, Katalyse und des Einflusses des Edukts konnte abgeleitet werden, daß es sich hiebei um eine nucleophile Substitution zweiter Ordnung am Carbonylzentrum des Harnstoffs handelt. Durch semiempirische Rechnungen mit Hilfe der MNDO Methode wurde der alternative Reaktionsmechanismus einer Fragmentierung untersucht.
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Hackl, K.A., Falk, H. The synthesis of N-substituted ureas II: Nucleophilic substitution of ureas at the carbonyl group. Monatsh Chem 123, 607–615 (1992). https://doi.org/10.1007/BF00816856
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DOI: https://doi.org/10.1007/BF00816856