Ozonolysis

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Ozonolysis is the cleavage of an alkene or alkyne with ozone to form compounds in which the multiple carbon-carbon bond has been replaced by a double bond to oxygen.[1][2][3] The outcome of the reaction depends on the type of multiple bond being oxidized and the workup conditions.

Ozonolysis of alkenes

Alkenes can be oxidized with ozone to form alcohols, aldehydes or ketones, or acids. In a typical procedure, ozone is bubbled through a solution of the alkene in dichloromethane at –78 °C until the solution takes on a characteristic blue color. This indicates consumption of the olefin. A workup reagent is then added to convert the intermediate ozonide to a carbonyl derivative. Reductive workup conditions are far more commonly used than oxidative conditions. The use of triphenylphosphine, zinc dust, or dimethyl sulfide produces aldehydes or ketones while the use of sodium borohydride produces alcohols. The use of hydrogen peroxide produces carboxylic acids. Recently, the use of amine N-oxides has been reported to produce aldehydes directly.[4] Other functional groups, such as benzyl ethers, can also be oxidized by ozone. It has been proposed that small amounts of acid may be generated during the reaction from oxidation of the solvent, so pyridine is sometimes used to buffer the reaction. Methanol is often used as a 1:1 cosolvent to facilitate timely cleavage of the ozonide. Azelaic acid and pelargonic acids are produced from ozonolysis of oleic acid on an industrial scale.

A widely used alternative method[5] for the ozonolysis of symmetrical alkenes allows differentially terminated hydrocarbons to be generated: with O3/MeOH/CH2Cl2; TsOH; NaHCO3; DMS, aldehyde and dimethyl acetal termini; with O3/MeOH/CH2Cl2; Ac2O, Et3N, methyl ester and aldehyde termini; with O3/MeOH/CH2Cl2; TsOH; Ac2O, Et3N, methyl ester and dimethyl acetal termini.

Reaction mechanism

In the generally accepted mechanism proposed by Rudolf Criegee in 1953,[6] the alkene and ozone form an intermediate molozonide in a 1,3-dipolar cycloaddition. Next, the trioxolane reverts to its corresponding carbonyl oxide and aldehyde or ketone in a retro-1,3-dipolar cycloaddition. The oxide and aldehyde or ketone react again in a 1,3-dipolar cycloaddition or produce a stable ozonide intermediate.

Evidence for this mechanism is found in isotopic labeling. When 17O-labelled benzaldehyde reacts with carbonyl oxides, the label ends up exclusively in the ether linkage of the ozonide.[7] There is still dispute over whether the molozonide collapses via a concerted or radical process; this may also exhibit a substrate dependence.

History

Ozonolysis was invented by Christian Friedrich Schönbein in 1840. Before the advent of modern spectroscopic teechniques, it was an important method for determining the structure of organic molecules. Chemists would ozonize an unknown alkene to yield smaller and more identififable fragments. The ozonolysis of alkenes is sometimes referred to as "Harries Ozonolysis," because some attribute this reaction to Carl Dietrich Harries.

Ozonolysis of alkynes

Ozonolysis of alkynes generally gives an acid anhydride or diketone product,[8] not complete fragmentation as for alkenes. A reducing agent is not needed for these reactions. The exact mechanism is not completely known.[9] If the reaction is performed in the presence of water, the anhydride hydrolyzes to give two carboxylic acids.

References

  1. Claus, R. E.; Schreiber, S. L. Org. Syn., Coll. Vol. 7, p.168 (1990); Vol. 64, p.150 (1986). (Article)
  2. Bailey, P. S.; Erickson, R. E. Org. Syn., Coll. Vol. 5, p.489 (1973); Vol. 41, p.41 (1961). (Article)
  3. Tietze, L. F.; Bratz, M. Org. Syn., Coll. Vol. 9, p.314 (1998); Vol. 71, p.214 (1993). (Article)
  4. (Org Lett 2006, 8, 3199-3201)
  5. (Schreiber, Org Syn v64)
  6. Criegee, R. Angew. Chem. Int. Ed. Engl. 1975, 87, 745-752. (doi:10.1002/anie.197507451)
  7. The Mechanism of Ozonolysis Revisited by 17O-NMR Spectroscopy Geletneky, C.; Berger, S. Eur. J. Org. Chem. 1998, 1625-1627. (Abstract)
  8. Bailey, P. S., chapter 2, in Ozonation in Organic Chemistry. Volume II: Nonolefinic Compounds. New York: Academic Press. 1982. ISBN 0120731029.
  9. Cremer, D. (2001). "The Ozonolysis of Acetylene-A Quantum Chemical Investigation". J. Am. Chem. Soc. 123 (25): 6127–6141. doi:10.1021/ja010166f. Unknown parameter |coauthors= ignored (help)

External Links

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