Oxone reaction with oximes

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) . 

A new method for conversion of oximes to the corresponding em-halonitro derivatives using NaCl or KBr with Oxone and wet basic alumina was reported (equation 64) °. When the reaction was carried out under the same conditions but by using wet neutral alumina, complex mixtures of compounds in which the parent ketone is the most abundant product (>50%), due to the oxidative deprotection of the oxime, was obtained. 

Nitrogen Compounds. The aqueous Oxone-acetone combination has been developed for the transformation of certain anilines to the corresponding nitrobenzene derivatives, as exemplified in eq 15. This process involves sequential oxidation steps proceeding by way of an intermediate nitroso compound. In the case of primary aliphatic amines, other reactions of the nitrosoalkane species compete with the second oxidation step (for example, dimerization and tautomerization to the isomeric oxime), thereby limiting the synthetic generality of these oxidations. An overwhelming excess of aqueous Oxone has been used to convert cyclohexylamine to nitrocyclohexane (eq 16)P... 

Sanford and coworkers have reported the use of Oxone in combination with palladium acetate for the oxime-ether directed C-H oxygenation of arenes (eq 111). A range of substituted arenes are tolerated under the reaction conditions and the use of Oxone rather than periodate-based oxidants afforded A -oxidized products in some cases. 

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