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Recently, there was a question which enquired about some oxygen rich compounds that burn themselves completely and thus not requiring any external atmospheric oxygen. The author came up with the compound $\ce{HC(=O)OOOH}$* which I am not sure if it exists. We already have peracids ($\ce{RC(=O)OOH}$) but I am not sure if there is any acid that has longer oxygen chain than peracid and I am also not sure if it remains acid any longer. Internet does not give me valid result. I know that long oxygen chains are unstable and prone to detonation (as are all oxygen rich compounds) but OP's compound* made me curious.

We have had previous discussions before mainly discussion hydrogen polyoxides, $\ce{HO_nH}$ (which has been detected and produced experimentally), peroxide linkage vs disulfide and bond energy comparison:

  1. Why does sulfur, but not oxygen, catenate?
  2. Are long oxygen molecules possible?
  3. Why is an S-S bond stronger than an O-O bond?
  4. Why are peroxides unstable but disulfide bridges considered stable? Why are esters stable but thiolesters are unstable?

However I am asking if there is any such corresponding organic compound that has been detected spectroscopically and that it exists even for some microseconds?

*the question was later edited to performic acid, thus its existence is already in question.
**When writing the formula, it looks like four oxygen atoms together in straight chain. However, one of the oxygen exist as carbonyl bond, thus compounds with three or more oxygen atoms in straight chain is in question.

Oscar Lanzi
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Nilay Ghosh
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  • Why don't you start with three in one chain? Or do I misunderstand the chain part? – Martin - マーチン Jan 09 '22 at 12:23
  • What's the successor of Beilstein Crossfire? – Karl Jan 09 '22 at 13:15
  • @Karl Oh the old times of MDL's Crossfire. The GUI underwent multiple revisions since then and now doesn't discern as much as «back then» between Beilstein and Gmelin when starting as Reaxys(TM) by Elsevier. It becomes a rare occasion to search from the terminal (like in the old days via STN/télésystèms Questel) ... – Buttonwood Jan 09 '22 at 13:52
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    Worth noting that peracids only contain two oxygens in a chain. – matt_black Jan 09 '22 at 14:30
  • One could ask PubChem (e.g., for four oxygen atoms, for five oxyen atoms, etc. However (my hunch), there are a bit too many properties labeled as computed property, e.g., for this one to think about them as stable/easy to handle in gram scale under ambient conditions. – Buttonwood Jan 09 '22 at 15:02
  • Something like F3COOOOCF3 should be possible, per analogy to FOOOOF, which is known. – Mithoron Jan 09 '22 at 17:38
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    For cautionary and entertaining articles on oxygen "chains', read Derek Lowe: https://www.science.org/content/blog-post/things-i-won-t-work-peroxide-peroxides , https://www.science.org/content/blog-post/not-do-ether-peroxides and https://www.realclearscience.com/blog/2015/06/foof_the_chemical_most_chemists_avoid.html . You'll get a real bang out of these. – DrMoishe Pippik Jan 09 '22 at 20:42
  • @Mithoron FOOOOF is known? What crazy lunatic made that (given how truly horrific FOOF already is)? ;-) – matt_black Jan 10 '22 at 12:44
  • @matt_black Well, guys making FOOF couldn't help themselves and experimented some more, obviously ;) – Mithoron Jan 10 '22 at 13:22
  • "I am not sure if it remains acid any longer." It does (if it doesn't blow up), but the extra oxygen atom breaks the conjugation with the carbonyl group and so the peroxy acid will be weaker than the normal carboxylic acid. – Oscar Lanzi Jan 10 '22 at 18:58
  • @matt_black https://www.researchgate.net/publication/237850820_AN_IMPROVED_PREPARATION_ANALYSIS_AND_SOME_PROPERTIES_OF_TETRAOXYGEN_DIFLUORIDE. – Oscar Lanzi Jan 10 '22 at 20:18

1 Answers1

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Three oxygen atoms in a row is more common than one might think. In the first stage of the reaction between alkenes and ozone, the ozone is attached to both ends of the double bond to form an intermediate with a five-membered ring (a molozonide). This ring contains the three oxygen atoms still in a row, before it breaks up:

enter image description here

(image source)

In addition, ionic ozonides, $\ce{R^+O_3^-}$, are known with some organic cations $\ce{R^+}$. These are made by metathesis reactions from the ozonides of heavier alkali metals, as described in this answer for $\ce{(CH_3)_4N^+O_3^-}$.

Oscar Lanzi
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