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DOI: 10.1055/sos-SD-031-01513

Rück-Braun, K.; Priewisch, B.Science of Synthesis, (2007311340.

Oxone is a triple salt, containing the same active oxidizing species as Caro's acid: the peroxymonosulfate ion. In contrast to Caro's acid, Oxone is stable and not prone to explosive decomposition but, like Caro's acid, it oxidizes anilines 61 in aqueous solution to nitrosobenzenes 62 (Scheme 32).[‌79‌,‌80‌] The use of a biphasic medium, for example dichloromethane/water, is advantageous as the nitroso compound is immediately extracted into the organic phase and is thus protected from further oxidation or condensation with an intermediate N-arylhydroxylamine. In general, only a small amount of the corresponding diaryldiazene oxide is formed as a byproduct. Overall this method gives very good yields for electron-deficient anilines, while electron-rich anilines, or anilines bearing functional groups that promote water solubility, afford the corresponding nitrosobenzenes in significantly lower amounts.[‌79‌]

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