Interaction between t-butyl hydroperoxide (I) and “positive halogen” compounds. part I. Intermediates in the reaction between I and CI2O

“positive halogen” compounds were found to induce the decomposition of t-butyl hydroperoxide (I) in the dark. In this Cl2O proved to be particularly effective, liberating oxygen from I instantaneously at 0°. At temperature between −80° and −30°, two oxygen-rich intermediates could be observed with the aid of NMR-spectroscopy. t-Butyl peroxyhypochlorite (But-O-O-Cl) was formed immediately; di-t-butyl trioxide (But[BOND]O[BOND]O[BOND]O[BOND]But) apparently resulted from a slower reaction, found to be promoted by alkali. By using a solution of di-t-butyl trioxide thus obtained, the polymerization of methyl acrylate could be initiated at a temperature as low as −20°.