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Alkene Reactions

By James Ashenhurst

Alkene Reactions: Ozonolysis

Last updated: March 26th, 2019

Today’s post represents not so much a pattern in alkene reactions, so much as it does a very common reaction that bears mentioning along with the rest. What makes this reaction special is that it does not simply break the carbon-carbon π bond, as we have been accustomed to seeing, but additionally breaks the C-C σ bond as well.

This type of reaction is known as oxidative cleavage [i.e. cleavage of bonds, occuring with oxidation] and the most prominent example of an oxidative cleavage reaction is ozonolysis. 

As mentioned on one Reagent Friday back in the day, ozone does more than absorb UV radiation in the upper atmosphere and cause breathing problems in traffic-clogged cities. It’s a powerful oxidant, and since its discovery in the mid 1800’s by (Schönbein) has found use in the cleavage of carbon-carbon multiple bonds.

Here’s the pattern for the reaction of alkenes with ozone:


Note that the carbon-carbon double bond is broken and we are forming a carbon-oxygen double bond on each of the two carbons that originally composed the alkene. The second step in ozonolysis is called the “workup”. There are two different types of “workup”, and the most common is referred to as “reductive workup”. In this step, we add a reducing agent (commonly zinc metal or dimethyl sulfide) that decomposes the intermediate formed at the end of the ozonolysis reaction (called an “ozonide” by the way). If you’re wondering where the third oxygen of ozone went – it’s now attached to what used to be our reducing agent (making either zinc oxide (ZnO) or dimethyl sulfoxide (DMSO). [For more details / mechanism everything is written out in this post.]

Using “reductive workup” preserves all other aspects of the molecule save the double bond. So if we start with, say, a trisubstituted alkene, as in the example below, we will end up with a ketone and an aldehyde. [What happens if the alkene carbon is attached to two hydrogens? It becomes formaldehyde, which is then further converted to carbon dioxide]


Note that although I’ve written (CH3)2S as the reductant here, it’s essentially interchangeable with Zn for our purposes.

An interesting consequence of ozonolysis is that if the alkene is within a ring, you end up with a chain containing two carbonyls:


If your molecule has multiple alkenes, then you will end up with more than two fragments. For many years ozonolysis was used as a method for the structure determination of unknown molecules. By analyzing the fragments it is then possible to deduce what the original structure was, through “stitching” together the fragments. [This was particularly important in the case of unsaturated molecules known as terpenes]. Here’s one example:


This isn’t the end of the story with ozonolysis. There’s a second type of workup that can be used, referred to as oxidative workup. Instead of using Zn or S(CH3)2, if we use the oxidant hydrogen peroxide [H2O2], any aldehydes that form will be oxidized to give carboxylic acids. Like in the example below – notice that the green C-H bond is oxidized to C-OH  [but all the other hydrogens remain intact ].


An alternative to using ozone for oxidative workup is to use the reagent KMnO, especially in the presence of hot acid; this will lead to the same result.

This is the last category of important alkene reactions we’ll cover for now in this series; in the next post we’ll wrap up the reactions of alkenes with a summary post.

NEXT POST: Summary of Alkene Addition Reactions


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Comment section

22 thoughts on “Alkene Reactions: Ozonolysis

  1. I had a question where it was a reaction map for turning a generic terminal alkyne into a generic aldehyde. I was going for using hydrogenization in the presence of Lindlar’s and ozonolysis.

    In the answer provided (one of many ways), the alkyne underwent ozonolysis with ozone followed by zinc in acid (h3O+) what would the purpose of the acid be?

    1. The acid helps to break up the intermediate ozonide – it protonates one of the oxygens and makes it a better leaving group, in a way similar to how acid helps to cleave acetals.

  2. I believe there is a typo- in the last mechanism, it is described c=o,-oh to be an “aldehyde” where it should be a carboxylic acid? (In oxidative workup, where the H is replaced with OH).

  3. when there is a cyclopentene attached to benzene ring, and ozonolysis is carried out then will the reaction take place only on pentene…? why does that happen..?

  4. If there are multiple alkenes within the original molecule but there is only one equivalent of O3, how do you determine which alkene to cleave and which to leave as is? Thanks!

    1. Hi – good question!
      Generally, the more highly substituted the alkene, the more electron rich it is, and the more reactive it will be towards O3 (sterics are not a significant factor in most cases).

      It’s possible to selectively ozonize an alkene assuming there is a significant difference in substitution pattern.

      For instance it’s possible to selectively ozonize a tetrasubstituted alkene in the presence of a disubstituted alkene. The trick is to use a dye as an indicator (an example is Sudan Red) that is intermediate in reactivity between the alkene you are trying to ozonize and the less reactive alkene. When the dye starts getting chewed up you will notice a color change and you can stop the reaction.

  5. I aspire to reach your level of orgo proficiency. Like for real, reading your answers to these questions is awesome. Orgo 2 final coming up for me

  6. What about Ozonolysis on O-xylene? I assume the reaction would take place at all of the alkenes? If this is the case, would it require 3 equivalents?

  7. Hi i was just wondering what the mechanism would be for example if i started with cyclohexene and used 03 and Me2S

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