Crystalline Di‐Tert‐Butyl Trioxide and Dicumyl Trioxide

Di‐tert‐butyl trioxide has been prepared at −50° by photolysis of solid di‐tert‐butyl diperoxymonocarbonate and, more conveniently, by the reaction of ozone in Freon 12 (CF2Cl2) or methyl chloride with either dissolved tert‐butyl hydroperoxide or suspended hydrated sodium tert‐butyl peroxide. A low‐temperature procedure for freeing the product from accompanying tert‐butyl alcohol and other impurities is described. The ozone ‐ sodium salt method has also been applied to the preparation of crystalline dicumyl trioxide. These trioxides have the properties previously observed in solution. They are unstable at temperatures above −30°. NMR spectra of the trioxides are reported and compared with those of related compounds. Approximate rate constants for the thermal decomposition of dicumyl trioxide are reported.