Dipropionyl peroxide, decomposition

Kolbe electrolysis also allows some comparisons with analogous homogeneous reactions with regard to dimerization, substitution, or addition reactions of the generated radicals. Photolytic or thermal decarboxylation of diacylperoxides is a source of alkyl radicals similar to those afforded by the Kolbe electrolysis. The anodic oxidation of propionate has been compared with the thermal decomposition of dipropionyl peroxide [28]. Examination of the yields shows that reaction between radicals is favored in the electrochemical process, whereas in peroxide decomposition hydrogen atom abstraction from the solvent or the substrate occurs to a higher extent. This illustrates the effect of the higher radical concentration at the electrode. 

Most of the isolated diacyl (including sulfonyl) peroxides are solids with relatively low decomposition temperatures, and are explosive, sensitive to shock, heat or friction. Several, particularly the lower members, will detonate on the slightest disturbance. Autocatalytic (self-accelerating) decomposition, which is promoted by tertiary amines, is involved [1]. Solvents suitable for preparation of safe solutions of diacetyl, dipropionyl, diisobutyryl and di-2-phenylpropionyl peroxides are disclosed [2], The class is reviewed, including hazards and safety measures [3], Cyclic diacyl peroxides are more stable, but scarcely to be trusted. Individually indexed compounds are ... 

---

See also in sourсe #XX -- [ , , , , ]

---