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Ammonolysis of morpholine‐2,5‐diones: participation of the primary amide group. Part 2
Author(s) -
Arcelli Antonio,
Bongini Alessandro,
Porzi Gianni,
Rinaldi Samuele
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1884
Subject(s) - chemistry , morpholine , amide , vicinal , transition state , primary (astronomy) , kinetics , reaction rate constant , computational chemistry , stereochemistry , reaction mechanism , density functional theory , leaving group , medicinal chemistry , group (periodic table) , organic chemistry , catalysis , physics , quantum mechanics , astronomy
The ammonolysis of three morpholine‐2,5‐dione derivatives was investigated and the mechanism ascertained by kinetic studies and theoretical calculations. The kinetics, followed by high‐performance liquid chromatography analysis, evidenced the presence of two intermediates, which were isolated and characterized. The ammonolysis occurs with a complex mechanism involving two consecutive reactions followed by two parallel ones. The second step of the whole reaction involves an anchimeric assistance of the primary amide group. The pseudo‐first‐order rate constants were calculated by appropriate equations, which describe the single steps of the process. Computational density functional theory investigations of vicinal primary amide group participation were performed using a model compound, and the transition states were generated. The theoretical calculations evidenced the essential role exerted by ammonia, which acts as a proton transfer. Copyright © 2011 John Wiley & Sons, Ltd.