Helvetica Chimica Acta p. 2399 - 2424 (2006)
Update date:2022-08-11
Topics:
Kirsch, Michael
Korth, Hans-Gert
Wensing, Angela
Lehnig, Manfred
Sustmann, Reiner
De Groot, Herbert
The reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration- and pH-dependent formation of N-nitrosomorpholine and N-nitromorpholine as reported in three previous papers ([25] [26] [14]) is basically confirmed. However, 13C-NMR spectroscopic product analysis shows that, in the absence of CO2, N-hydroxymorpholine is, at pH≥7, the major product of this reaction, even under anaerobic conditions. The formation of N-hydroxymorpholine has been overlooked in the three cited papers. Additional (ring-opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholine-derived aminyl and α-aminoalkyl radicals. This is further supported by EPR-spectrometric detection of morpholine-derived nitroxide radicals, i.e., morpholin-4-yloxy radicals. N-Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite-derived N2O4. 15N-CIDNP Experiments establish that, in the presence of CO2, N-nitro- and C-nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28±2% ) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals.
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