Came across a question that talked about fragmentation of peroxyesters, about the peroxide linkage of course. After the fragmentation of the peroxyester was done, it gave out three products (2 being free radicals, and the other being carbon dioxide)

One of the products(i.e. free radical), went under a reaction (with itself) and gave two products, one being another free radical and the other being a carbonyl compound. I am unsure about the mechanism.

enter image description here

Here's what I thought: The single bond between the C1 and C2 will cleave in a homolytic manner. The (now) unpaired electron on C1 will combine with the unpaired electron of oxygen to form a $\pi$ bond. Also, the unpaired electron will remain on C2.

Why am I not sure about my reasoning? Because why would a homolytic cleavage take place between C1 and C2 after all?

Any hints or tips would be highly appreciated.

  • $\begingroup$ In what situation it's supposed to be happening? $\endgroup$
    – Mithoron
    Mar 19, 2020 at 0:45

1 Answer 1


You seem unsure about the homolysis between C1 and C2, but I speculate to consider the product's stability in this suggested reaction:

enter image description here

For one, two previously unpaired electrons form a $\pi$ bond in acetone. For the other, you form a benzyl radical which may be described in more than one mesomeric form, for example for a radical bromination reaction of toluene. Plus the neuter tropyl radical, the seven membered ring structure on the bottom right, result of a rearrangement.

Of course, the benzyl radical won't be persistent, eventually either looses a hydrogen, or combines with an other radical to form a closed shell molecule.


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