KINETICS AND MECHANISM OF ACID HYDROLYSIS OF PEROXYKETALS

Article abstract of DOI:10.1007/BF00958834

The kinetics of hydrolysis of aliphatic ketone di-tert-butylperoxyketals R¹R², R¹=CH3, CH3; CH3, C2H5; CH3, n-C3H7; CH3, n-C6H13; CH3, i-C5H10; CH3, i-C4H9; C2H5, i-C3H7; n-C4H9, n-C4H9; CH3, C6H5-CH2, in dioxane in the presence of H2SO4 were investigated by IR spectroscopy.It was found that the reaction is reversible and takes place according to the equation R¹R²C(OOC(CH3)3)2 + H2O <*> R¹R²=O + 2 HOOC(CH3)3.The proposed mechanism of hydrolysis includes the fast, quasiequilibrium formation of protonated peroxyketal and subsequent formation of the alkylperoxycarbenium ion.A three-parameter correlation equation is proposed for describing the initial rates of hydrolysis of R¹R²C(OO-t-Bu)2 peroxyketals.