Why Would You Do That?! – Making cyclic peroxides from triketones

Not to steal any thunder from Derek Lowes’ Things I Won’t Work With, I would like to draw attention to a paper that simply made me exclaim, “Why would you do that?!”

Selective Synthesis of Cyclic Peroxides from Triketones and H2O2

And of course the Russians are up to the most bat-sh*t insane things again. Quick primer on why this set off alarm bells: if you’re not aware, the explosive used in the 2001 shoe bomb plot was triacetone triperoxide, also known as TATP. These compounds are why chemists are taught never to wash flasks that recently contained hydrogen peroxide with acetone; the mixture easily and rapidly forms the dimeric and trimeric acetone peroxides shown to the right. Both of these explode with vigor, and should be avoided at all costs because they can literally take down planes. Want to know why you’re limited to specific volumes of liquids on planes? It’s because that’s the volume of acetone and hydrogen peroxide one would need to inflict enough damage on a jumbo jet to take it down. For those who haven’t flown in a while, it’s not much.

Peroxides of acetone. Danger! Crazy explosives!

So why in the heck were these guys making it?

The interest in the synthesis of radical
polymerization initiators and drugs gave impetus to the
development of methods for the synthesis of peroxides with
the use of carbonyl compounds, their derivatives, and H2O2
the starting reagents.

Now, maybe these aren’t so bad. The authors do report refluxing their compounds in ethanol for extended periods of time, so perhaps the extra mass and being tied up in a ring stabilizes them, but if I were a new graduate student being sold this project, I would be cautious. Remember, the authors who published on FOOF reported storing that, but I don’t think I would ever want to make it, let alone store it, so perhaps some reading between the lines is necessary for this paper.

Thoughts? Would you make these? Is it worth risking your precious, precious fingers?

Damn Russians, why do you always have to make us Americans look like wusses?


6 thoughts on “Why Would You Do That?! – Making cyclic peroxides from triketones

    1. Honestly, I keep an RSS feed of ACS journals and saw polyperoxide –typo, just one peroxide!–
      and, upon picking my jaw off the floor, proceeded to read the paper. No, I wasn’t seeking it, but rather the article found me!

  1. I’m not convinced how mental it is. It’s only a single peroxide group (the others are acetals, not exactly the most explosive in the world)
    Have you ever worked with TBHP as a radical initiator or epoxidation agent (it’s the oxidant in the Sharpless Asymmetric Epoxidation) – generally to be found in most lab fridges? Plus think of all those natural products with a single epoxide in a polycyclic framework.

    It’s all very well to be aware of hazards, but it’s also worthwhile thinking about context…

    1. That’s a really good point, esp. referring to the natural products with endoperoxides. I think I said “polyperoxide” in one of my responses, but that was a typo, which I should probably fix.

      That said, TBHP isn’t exactly the safest thing in the world; it’s orders of magnitude better for your health than H2O2, but it’s sort of like nBuLi is to tBuLi as TBHP is to H2O2. As I pointed out in the article, these things are probably pretty OK, since the authors reflux them in ethanol for extended periods of time without blowing themselves up, and honestly some of these things get a bad rap (as a guy who works with diazo compounds on a regular basis, there are certain functional groups that are unnecessarily discriminated against). It makes sense that these would be more stable than H2O2, since the reaction to make them is basically a thermodynamic sink from H2O2 to the desired products, and as long as that’s handled well, then I think it’s altogether OK.

      tl;dr I think you’re right, overall. I’m not sure I’m totally sold on the safety of these compounds, but I would certainly be willing to give them a try, were they relevant to something I was working with!

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