Thermal decomposition of allylbenzene ozonide

Thermal decomposition of allylbenzene ozonide (ABO) at 98{degree}C in the liquid phase yields toluene, bibenzyl, phenylacetaldehyde, formic acid, and (benzyloxy)methyl formate as major products; benzyl chloride is formed when chlorinated solvents are employed. These products, as well as benzyl formate, are formed when ABO is decomposed at 37{degree}C. When the decomposition of ABO is carried out in the presence of 1-butanethiol, the product distribution changes: yields of toluene increase, no bibenzyl is formed, and decreases in yields of (benzyloxy)methyl formate, phenylacetladehyde, and benzyl chloride are observed. The decomposition of 1-octene ozonide (OTO) also was studied for comparison. The activation parameters for both ABO and OTO are similar (28.2 kcal/mol, log A = 13.6 and 26.6 kcal/mol, log A = 12.5, respectively); these data suggest that ozonides decompose by homolysis of the O-O bond, rather than by an alternative synchronous two-bond scission process. When ABO is decomposed at 37{degree}C in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO) or 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M{sub 4}PO), ESR signals are observed that are consistent with the trapping of benzyl and other carbon- and oxygen-centered radicals. A mechanism for the thermal decomposition of ABO that involves peroxide bond homolysis and subsequent {beta}-scission is proposed. Thus, Criegee ozonides decompose to give free radicals at quite modest temperatures.