Ammonolysis of morpholine‐2,5‐diones: participation of the primary amide group. Part 2 |
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Authors: | Antonio Arcelli Alessandro Bongini Gianni Porzi Samuele Rinaldi |
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Institution: | 1. Dipartimento di Chimica “G. Ciamician”, , 40126 Bologna, Italy;2. Dipartimento I.S.A.C., Università Politecnica delle Marche, , 60131 Ancona, Italy |
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Abstract: | 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. |
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Keywords: | ammonolysis anchimeric assistance computational investigations kinetic investigations morpholine‐2 5‐diones primary amide group participation |
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