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- W2003107389 abstract "Pathways for oxidation of the parent nitrosoamine 2, nitrosodimethylamine 3, and anti- nitrosoethylmethylamine 4 by the parent dioxirane 1 have been explored computationally using the B3LYP hybrid density functional theoretical method in conjunction with the 6-31G* and 6-311+G** basis sets. Oxygen transfer from 1 to the nitrogen of the NO group (NO oxidation), yielding nitroamines 5,7, and 10, has the lowest activation barrier (15, 12.8, and 12 kcal mol -1 for 2, 3, and anti-4, respectively). Oxidation of the amine nitrogen (N oxidation) in 2, 3 leads to nitric oxide and nitroxyl radicals 6, 8 and is characterized by the highest activation energy: 28.5 kcal mol -1 for 2, 22.3 kcal mol -1 for 3. The potential barrier to hydroxylation of the methyl groups in 3 (CH oxidation) is intermediate - ca. 19 kcal mol -1 . Introduction of a methyl group to the carbon reaction centre decreases the activation barrier of the anti-CH oxidation by 2-3 kcal mol -1 . In 3, a gas-phase small preference for anti-CH oxidation over syn-CH oxidation, 0.1 kcal mol -1 , is predicted to increase dramatically to 4.7 kcal mol -1 when the reaction is carried out in a dielectric medium (acetone, IPCM model). In general, polar solvents (CH 2 Cl 2 , acetone) lower the activation barriers for the NO, N, and CH oxidations, more so for the species of higher polarity than those of lower polarity (reactive complexes (1+3), (1+anti-4), transition state anti,syn-TS CH (1+4)]. However, the chemoselectivity (E a NO <E a anti -CH <E a syn -CH <E a N ) in the polar solvents is predicted to be the same as in the gas phase.Key words: dioxirane, nitrosoamines, oxidation, ab initio, omputation." @default.
- W2003107389 created "2016-06-24" @default.
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- W2003107389 date "1999-01-01" @default.
- W2003107389 modified "2023-09-25" @default.
- W2003107389 title "Dioxirane oxidation of nitrosoamines. An ab initio study" @default.
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- W2003107389 doi "https://doi.org/10.1139/v98-217" @default.
- W2003107389 hasPublicationYear "1999" @default.
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