Dioxiranes

The name of this class of compounds is determined by the composition of its hydrocarbon radicals, for example, dioxirane ( formula I ), dimethyldioxirane ( formula II ), cyclohexanone dioxirane ( formula III ).

The most convenient and widely used method for the synthesis of dioxiranes is the oxidation of ketones (for example, acetone ) with a peroxosulfuric acid salt ( Caro acid ) H ₂ SO ₅ oxone (KHSO ₄ · 2KHSO ₅ · K ₂ SO ₄ ):

A solution of dioxirane in the initial ketone is obtained, which is stored at low temperatures.

Other methods for the preparation of dioxiranes have not received practical application.

Decay

Dioxirans are thermally unstable compounds. Their decay proceeds by a complex mechanism. The reaction is catalyzed by impurities of heavy metal ions, as well as decay products. The decomposition mechanism depends on such parameters as temperature, dissolved oxygen content, and the presence of impurities. The following decay paths are possible:

• Dimerization
• Decay through the enol form
• Radically chain decay of an OO bond
• Isomerization
• Induced Decomposition

Oxidizing properties

Due to the presence of the peroxide bond of OO, dioxiranes have oxidizing properties. Many oxidation reactions with dioxiranes of organic compounds are highly selective and proceed under mild conditions:

• Alkanes are converted to alcohols
• Alkenes are converted to epoxy compounds
• Secondary alcohols are oxidized to ketones
• Phenols form quinones
• Amines are converted to nitro compounds
• Sulfides are subsequently converted to sulfoxides and sulfones

• V.P. Kazakov, A.I. Voloshin, D.V. Kazakov. Dioxirans: from oxidative transformations to chemiluminescence // Advances in Chemistry 68 (4) 1999, pp. 283-317
• V. L. Antonovsky, S. L. Hursan. Physical chemistry of organic peroxides. - M.: IKC "Akademkniga", 2003. - 391 p.