Reagent Friday: Ozone (O3)
Last updated: January 29th, 2020 |
Ozone (O3), A Powerful Oxidant In Organic Chemistry
Ozone is a molecule that most people are familiar with hearing about, either because it is missing (in the high atmosphere, where it absorbs UV radiation) or because it is present (as a toxic component of smog). But ozone is also very useful in a chemistry lab.
What it’s used for: As a reagent, ozone is used to cleave alkenes and alkynes to give carbonyl compounds such as aldehydes, ketones, and carboxylic acids. The type of products obtained depends upon the “workup” used – that is, the way it is treated after the reaction is over. The process of breaking a carbon-carbon multiple bond to form carbonyl compounds is called “oxidative cleavage”.
Ozone (O3) In the Oxidative Cleavage Of Alkenes (With Reductive Workup )
When alkenes are treated with ozone and subjected to “reductive workup” with either zinc (Zn) or dimethyl sulfide (Me2S) [triphenylphosphine (Ph3P) also sees use], the carbon-carbon double bond is cleaved to form ketones or aldehydes, depending on the structure of the alkene.
Ozone (O3) In The Oxidative Cleavage Of Alkenes (With Oxidative Workup)
Oxidative Cleavage Of Alkynes
Mechanism For The Oxidative Cleavage Of Alkenes With O3 (Ozone) And Reductive Workup With Zn Or DMS
The mechanism for oxidative cleavage is a fairly lengthy one and the actual details of the experiments used to determine the proposed mechanism are fascinating, but for our purposes we’ll just mention that the first step is referred to as a “cycloaddition”, (sometimes a “3+2 cycloaddition”) resulting in the formation of a 5 membered ring (“molozonide”). The molozonide is unstable, and undergoes fragmentation followed by rearrangement to give an isomeric 5-membered ring called an “ozonide”.
At the temperatures at which these reactions are done (usually dry-ice/acetone, or –78°C) ozonides are fairly stable, but will break down to form acyclic compounds when warmed. To obtain the final products (as well as to get rid of any excess ozone), the workup is performed. In reductive workup, a reagent is added that will cleave the O-O bond. Warming of the solution then results in the desired aldehyde/ketone. In oxidative workup, the ozonide is allowed to decompose in the presence of hydrogen peroxide, which will oxidize aldehydes to carboxylic acids. (This is already a long post, so the images will have to wait for now.)
Ozonolysis is discussed in more detail here (See post – Alkene Reactions: Ozonolysis)
Real life advice: One of the cool things about using ozone in the lab is that it has a very distinctive beautiful blue color. Back in the day, I used an old-school ozone generator to bubble ozone through my reaction solution, and when there was no more of the starting alkene left, the blue color of the excess ozone served as an indicator that the reaction was done. The smell is very distinctive too – sharp and metallic, a smell you might recognize if you’ve stood around transmission power lines. In fact, Schönbein, who discovered ozone in 1840, coined the name “ozone” from the
German Greek “ozein”, meaning “to smell”. Pretty cool that one atom make such a difference to the nose! (although one wonders how much of it is merely the sensation of your olfactory receptors getting zapped).
P.S. You can read about the chemistry of ozone and more than 80 other reagents in undergraduate organic chemistry in the “Organic Chemistry Reagent Guide”, available here as a downloadable PDF. The Reagents App is also available for iPhone, click on the icon below!
(Advanced) References and Further Reading
- Ueber die Einwirkung des Ozons auf organische Verbindungen
Just. Lieb. Ann. Chem. 1905, 343 (2-3), 311-344
The first paper describing the oxidative cleavage of unsaturated compounds with ozone in solution.
I. Smith, F. L. Greenwood, and O. Hudrlik
Org. Synth. 1946 26, 63
This procedure from Organic Syntheses, a source of reliable, reproducible and independently tested organic chemistry laboratory experimental procedures, provides a detailed explanation of how to build a laboratory ozonizer.
- The Preparation of Aldehydes, Ketones, and Acids by Ozone Oxidation
Albert L. Henne and Philip Hill
Journal of the American Chemical Society 1943 65 (5), 752-754
This paper shows that carboxylic acids are formed in good yields from aldehydes when the ozonolysis reaction mixture is worked up in the presence of excess hydrogen peroxide.
- Notes- A Convenient Method for Reduction of Hydroperoxide Ozonation Products
Knowles and Q. Thompson
The Journal of Organic Chemistry 1960 25 (6), 1031-1033
Although the current practice is to use dimethyl sulfide in a reductive ozonolysis workup, trimethyl phosphite can also be used, as this paper from Nobel Laureate W. S. Knowles demonstrates.
- OZONOLYTIC CLEAVAGE OF CYCLOHEXENE TO TERMINALLY DIFFERENTIATED PRODUCTS: METHYL 6-OXOHEXANOATE, 6,6-DIMETHOXYHEXANAL, METHYL 6,6-DIMETHOXYHEXANOATE
Ronald E. Claus and Stuart L. Schreiber
Org. Synth. 1986, 64, 150
This procedure in Organic Syntheses demonstrates how ozonolysis can be used to quickly generate differentiated bifunctional compounds.
- Mechanism of Ozonolysis
Dr. Rudolf Criegee
Angew. Chem. Int. Ed. 1975, 14 (11), 745-752
This is an account by Prof. Rudolf Criegee on work done towards determining the mechanism of ozonolysis. Criegee himself carried out extensive work in this area – the ‘Criegee intermediate’ in ozonolysis is named after him.The following papers are further mechanistic studies on ozonolysis:
- New evidence in the mechanism of ozonolysis of olefins
G. Klopman and C. M. Joiner
Journal of the American Chemical Society 1975 97 (18), 5287-5288
- Mechanism of ozonolysis. (a) Microwave spectra, structures, and dipole moments of propylene and trans-2-butene ozonides. (b) Orbital symmetry analysis
Robert P. Lattimer, Robert L. Kuczkowski, and Charles W. Gillies
Journal of the American Chemical Society 1974 96 (2), 348-358
- Microwave and mass spectral studies of the ozonolyses of ethylene, propylene, and cis- and trans-2-butene with added oxygen-18 formaldehyde and acetaldehyde
Charles W. Gillies, Robert P. Lattimer, and Robert L. Kuczkowski
Journal of the American Chemical Society 1974 96 (5), 1536-1542