Autoxidation

Autoxidation is any oxidation that occurs in presence of oxygen. The term is usually used to describe the degradation of organic compounds in air (as a source of oxygen). Autoxidation produces hydroperoxides and cyclic organic peroxides. These species can react further to form many products. The process is relevant to many phenomena including aging, paint, spoilage of foods, degradation of petrochemicals, and the industrial production of chemicals. Autoxidation is important because it is a useful reaction for converting compounds to oxygenated derivatives, and also because it occurs in situations where it is not desired (as in the destructive cracking of the rubber in automobile tires or in rancidification).[1]

A classic example of autoxidation involves the conversion of diethyl ether to its hydroperoxide. It can be considered to be a slow, flameless combustion of materials by reaction with oxygen.

Although virtually all types of organic materials can undergo air oxidation, certain types are particularly prone to autoxidation, including unsaturated compounds that have allylic or benzylic hydrogen atoms; these materials are converted to hydroperoxides by autoxidation.

Mechanism

Autoxidation is a free radical chain process. Such reactions can be divided into three stages: chain initiation, propagation, and termination.[2] Initiation is a broad term for any process, often ill-defined, that generates a free radicals of sufficient reactivity to undergo the subsequent step. For example, free radicals can be produced purposefully by the decomposition of a radical initiator, such as benzoyl peroxide. In some cases, initiation occurs by a process that is not well understood but is thought to be the spontaneous reaction of oxygen with a material with a readily abstractable hydrogen. Destructive autoxidation processes also are initiated by pollutants such as those in smog.

Once the free radical has formed, it react with O₂ to give a hydroperoxyl (ROO^.) intermediate. For organic radicals, this step is very rapid. The hydroperoxyl is itself a radical and thus capable of abstracting an H atom from a weak C-H bond. The chain termination reactions then occurs in which free radicals collide and combine their odd electrons to form a new bond.

Chain initiation

${\displaystyle {\begin{array}{l}{\ce {{ROOH}+RH->[{\overset {}{\ce {energy}}}]{RO.}+{.OH}+RH->{RO.}+{H2O}+R.}}\\{\ce {{RO.}+RH->[{\ce {H-abstraction}}]{R.}+ROH}}\end{array}}}$

Chain propagation

${\displaystyle {\begin{array}{l}{\ce {{R.}+ O2 ->[{\ce {fast}}] ROO.}}\\{\ce {{ROO.}+ RH ->[{\ce {H-abstraction}}] {ROOH}+ .R}}\end{array}}}$

Chain termination

${\displaystyle {\ce {2 ROO. -> {2 RO.}+ O2 -> {ROH}+ {QO}+ O2}}}$

Source of alcohol and ketone[3]

${\displaystyle {\begin{array}{l}{\ce {{ROOH}+ {ROO.}-> {ROOH}+ {Q.}OOH -> {ROOH}+ {QO}+ .OH}}\\{\ce {{ROOH}+ {QO}+ {.OH}+ RH -> {ROOH}+ {QO}+ {H2O}+ R. -> {RO.}+ {ROH}+ {QO}+ H2O}}\end{array}}}$

In steady state, the concentration of chain-carrying radicals is constant, thus the rate of initiation equals the rate of termination.

${\displaystyle \mathrm {r_{init}=k_{init}\cdot [ROOH]=k_{term}\cdot [ROO^{\cdot }]^{2}} }$

${\displaystyle \mathrm {r_{prop}=k_{prop}\cdot [RH]\cdot [ROO^{\cdot }]=k_{prop}\cdot [RH]\cdot {\sqrt[{\,}]{\frac {k_{init}}{k_{term}}}}\cdot {\sqrt[{\,}]{[ROOH]}}} }$

Autoxidations in industry

Autoxidation is a process of enormous economic impact, since all foods, plastics, gasolines, oils, rubber, and other materials that must be exposed to air undergo continuous destructive reactions of this type. All plastics and rubber and most processed foods contain antioxidants to protect them against the attack of oxygen.

In the chemical industry many chemicals are produced by autoxidation:

• in the cumene process phenol and acetone are made from benzene and propylene
• the autoxidation of cyclohexane yields cyclohexanol and cyclohexanone.[4]
• p-xylene is oxidized to terephthalic acid
• ethylbenzene is oxidized to ethylbenzene hydroperoxide, an epoxidizing agent in the propylene oxide/styrene process POSM.

Autoxidation in food

It is well known that fats become rancid, even when kept at low temperatures. This is especially true for polyunsaturated fats.[5]

The complex mixture of compounds found in wine, including polyphenols, polysaccharides, and proteins, can undergo autoxidation during the aging process. Simple polyphenols can lead to the formation of B-type procyanidins in wines[6] or in model solutions.[7] This is correlated to the browning color change characteristic of this process.[8]

This phenomenon is also observed in carrot puree.[9]

References

1. H. Yin, N. A. Porter (2005). "Forum Review: New Insights Regarding the Autoxidation of Polyunsaturated Fatty Acids". Antioxidants & Redox Signaling. 7 (1–2): 170–84. doi:10.1089/ars.2005.7.170. PMID 15650406.CS1 maint: uses authors parameter (link)
2. K. U. Ingold (1961). "Inhibition of the Autoxidation of Organic Substances in the Liquid Phase". Chem. Rev. 61 (6): 563–589. doi:10.1021/cr60214a002.
3. I. Hermans, T.L. Nguyen, P.A. Jacobs, J. Peeters, ChemPhysChem 2005, 6, 637-645.
4. I.V. Berezin, E.T. Denisov, The Oxidation of Cyclohexane, Pergamon Press, New York, 1996.
5. Lipid peroxidation in culinary oils subjected to thermal stress. H. Ramachandra Prabhu, Indian Journal of Clinical Biochemistry, 2000, Volume 15, Number 1, 1-5, doi:10.1007/BF02873539
6. Tandem mass spectrometry of the B-type procyanidins in wine and B-type dehydrodicatechins in an autoxidation mixture of (+)-catechin and (−)-epicatechin. Weixing Sun, Miller Jack M., Journal of mass spectrometry, 2003, vol. 38, no4, pp. 438-446
7. Identification of autoxidation oligomers of flavan-3-ols in model solutions by HPLC-MS/MS. Fei He, Qiu-Hong Pan, Ying Shi, Xue-Ting Zhang, Chang-Qing Duan, Journal of Mass Spectrometry, Volume 44 Issue 5, Pages 633 - 640, 2008
8. Nonenzymic Autoxidative Reactions of Caffeic Acid in Wine. Johannes J. L. Cilliers 1 and Vernon L. Singleton, Am. J. Enol. Vitic. 41:1:84-86, 1990.
9. Phenolic Autoxidation Is Responsible for Color Degradation in Processed Carrot Puree. Talcott S. T. and Howard L. R., J. Agric. Food Chem., 1999, 47 (5), pp 2109–2115.