The Thermal Decomposition of Cyanodiphenylmethyl t-Butyl Peroxide An Example of C–O Bond Scission

Abstract

The thermal decomposition of cyanodiphenylmethyl t-butyl peroxide was investigated. The peroxide is abnormally stable and decomposes slowly at 130–135 °C, and the main reaction product is tetraphenylsuccinonitrile. A main reaction path including the C–O bond scission, in contrast to the case of triphenylmethyl t-butyl peroxide, is proposed.

Thermolysis of organic peroxides in solution

“…tert-Butyl diphenylcyanomethyl peroxide undergoes decomposition in boiling cumene 25 to give acetone and tert-butyl alcohol in low yields (5% and 16%, respectively); tetraphenylsuccinonitrile is formed as the main product.…”

“…111 Intramolecular hydrogen bonds can be formed in hydrotrioxides that are derivatives of alcohols, esters and acetals containing an additional oxygen atom at the a-C atom. For these compounds, the molecular mechanism for the decomposition [reaction (25)] is feasible. 113 However, the experimental data altogether are more consistent with the radical mechanism of ROOOH decomposition; its first step includes the homolysis of the RO7OOH bond [reaction (26)] (the cleavage of ROOOH was demonstrated for a-hydrotrioxyethanol).…”