Secondary amines, dioxirane oxidation

Aliphatic primary amines are known to be oxidized by dimethyl dioxiranes to various products such as oximes, nitroso dimers, nitroalkanes, nitrones and oxazrridines under various conditions depending upon the oxidation reaction . In contrast, when secondary amines lacking a-hydrogens are allowed to react with Oxone and PTC in buffered acetone solution at 0 °C, nitroxides are obtained in good yields in a few minutes (equation 61) . 

The oxidation of secondary amines with no a-hydrogen atoms leads to hydroxy-lamines, but excessive dioxirane may further oxidize the hydroxylamines to the corresponding nitroxyl radical. For example, when a slight excess of isolated DMD is employed, 2,2,6,6-tetramethylpiperidin-4-ol (15) is quantitatively transformed into the hydroxylamine... 

All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyl dioxirane." Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone, various peroxyacids," MeRe03/H202,"" Oxone ," ° tcrt-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds, and sodium perborate." ... 

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