Ozone with tert-butyl hydroperoxide

The Reaction of Ozone with tert-Butyl Hydroperoxide. An MAH Hydrogen Atom Transfer from Oxygen... 

Analysis of the reaction of ozone with tert-butyl hydroperoxide in CHCI3, CCla, or CFCI3 as solvents at temperatures from 24 to -60 showed that the products are tert-butyl alcohol, acetone, water, and di-tai t-butyl peroxide (44,44a) The reaction scheme, shown in eqs 35-43, rationalizes these products as resulting from free radical reactions of ozone and the hydroperoxide, where T tert-Ci Ylg. 

The atmospheric lifetime of tert-butyl hydroperoxide with respect to reaction with OH radicals is of the order of few days. Similar to other hydroperoxides, photolysis could also have an important contribution to the atmospheric removal of tert-butyl hydroperoxide. The reaction of OH with tert-butyl hydroperoxide is expected to proceed through H-atom abstraction from the —OOH group to give (CH3)3C02 radicals which will react with NO, other peroxy radicals, and ozone as suggested in the previous sections for methyl and ethyl peroxy radicals. 

Elimination reactions leading to olefins are usually performed on the corresponding selenoxides 3 9,1 12) (Scheme 2 a). These are often unstable and decompose at room temperature to olefins and selenenic acid (further oxidized to the more stable seleninic acid by excess of oxidant). Hydrogen peroxide in water-THF, ozone and further treatment with an amine or tert-butyl hydroperoxide without or with alumina proved to be the method of choice for such a synthesis of olefins. The reaction is reminiscent of the one already described with aminoxides or sulfoxides 22) and occurs via a syn elimination of the seleninyl moiety and the hydrogen attached to the P-carbon atom. However it takes place under smoother conditions. 

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