The regioselective oxidation of N-phenylmorpholine by ozone in dichloromethane or acetonitrile produced a lactam and a diformylderivative. These products derive from the selective attack of ozone at the heterocyclic ring in one of the two non-equivalent reactive carbons. The reaction mechanism has been investigated by DFT calculations, which show that the reaction occurs through the insertion of ozone at the carbon-hydrogen bond of a methylene group of the morpholine ring. The regioselectivity is due to the significantly lower energy barrier calculated for the attack of ozone α to nitrogen than α to oxygen. In addition, the energy barrier decreases with increasing the polarity of the solvent, explaining the higher conversions observed for the reaction carried out in acetonitrile than in dichloromethane.

Suarez Bertoa, R., Saliu, F., Bruschi, M., & Rindone, B. (2012). Reaction products and mechanism of the regioselective oxidation of N-phenylmorpholine by ozone. TETRAHEDRON, 68(39), 8267-8275 [10.1016/j.tet.2012.07.055].

Reaction products and mechanism of the regioselective oxidation of N-phenylmorpholine by ozone

SALIU, FRANCESCO;BRUSCHI, MAURIZIO
;
2012

Abstract

The regioselective oxidation of N-phenylmorpholine by ozone in dichloromethane or acetonitrile produced a lactam and a diformylderivative. These products derive from the selective attack of ozone at the heterocyclic ring in one of the two non-equivalent reactive carbons. The reaction mechanism has been investigated by DFT calculations, which show that the reaction occurs through the insertion of ozone at the carbon-hydrogen bond of a methylene group of the morpholine ring. The regioselectivity is due to the significantly lower energy barrier calculated for the attack of ozone α to nitrogen than α to oxygen. In addition, the energy barrier decreases with increasing the polarity of the solvent, explaining the higher conversions observed for the reaction carried out in acetonitrile than in dichloromethane.
Articolo in rivista - Articolo scientifico
Ozone, Oxidation, DFT Calculations, Reaction Mechanism
English
8267
8275
9
Suarez Bertoa, R., Saliu, F., Bruschi, M., & Rindone, B. (2012). Reaction products and mechanism of the regioselective oxidation of N-phenylmorpholine by ozone. TETRAHEDRON, 68(39), 8267-8275 [10.1016/j.tet.2012.07.055].
Suarez Bertoa, R; Saliu, F; Bruschi, M; Rindone, B
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/37694
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