Free-radical reaction
A free-radical reaction is any chemical reaction involving free radicals. This reaction type is abundant in organic reactions. Two pioneering studies into free radical reactions have been the discovery of the triphenylmethyl radical by Moses Gomberg (1900) and the lead-mirror experiment[1] described by Friedrich Paneth in 1927. In this last experiment tetramethyllead is decomposed at elevated temperatures to methyl radicals and elemental lead in a quartz tube. The gaseous methyl radicals are moved to another part of the chamber in a carrier gas where they react with lead in a mirror film which slowly disappears.
When radical reactions are part of organic synthesis the radicals are often generated from radical initiators such as peroxides or azobis compounds. Many radical reactions are chain reactions with a chain initiation step, a chain propagation step and a chain termination step. Reaction inhibitors slow down a radical reaction and radical disproportionation is a competing reaction. Radical reactions occur frequently in the gas phase, are often initiated by light, are rarely acid or base catalyzed and are not dependent on polarity of the reaction medium.[2] Reactions are also similar whether in the gas phase or solution phase.[3]
Kinetics
The chemical kinetics of a radical reaction depend on all these individual reactions. In steady state the concentrations of initiating (I.) and terminating species T. are negligent and rate of initiation and rate of termination are equal. The overall reaction rate can be written as:[4]
with a broken-order dependence of 1.5 with respect to the initiating species.
The reactivity of different compounds toward a certain radical is measured in so-called competition experiments. Compounds bearing carbon–hydrogen bonds react with radicals in the order primary < secondary < tertiary < benzyl < allyl reflecting the order in C–H bond dissociation energy[4]
Many stabilizing effects can be explained as resonance effects, an effect specific to radicals is the captodative effect.[5]
Reactions
Examples of reactions involving free radicals include:
- Free-radical substitution,[6] for instance free-radical halogenation[7] and autoxidation.[8]
- Free-radical addition reactions[9]
- Intramolecular free radical reactions (substitution or addition) such as the Hofmann–Löffler reaction[10] or the Barton reaction[11]
- Free radical rearrangement reactions, which are less common than carbocation rearrangements[12] due to the instability of the 1,2-rearrangement[12][13] and restricted to certain functional groups (e.g aryl, vinyl).[13][14]
- Fragmentation reactions or homolysis,[15] for instance the Norrish reaction,[16] the Hunsdiecker reaction[17] and certain decarboxylations.[18] For fragmentations taking place in mass spectrometry see mass spectrum analysis.
- Electron transfer. An example is the decomposition of certain organic peroxides by Cu(I) which is a one-electron reduction reaction forming Cu(II), an alkoxy oxygen radical and a carboxylate.[19] Another example is Kolbe electrolysis.[20]
- Radical-nucleophilic aromatic substitution,[21] a special case of nucleophilic aromatic substitution.
- Carbon–carbon coupling reactions, for example manganese-mediated coupling reactions.[22]
- Elimination reactions[23]
Free radicals can be formed by photochemical reaction and thermal fission reaction or by oxidation reduction reaction. Specific reactions involving free radicals are combustion, pyrolysis and cracking.[24] Free radical reactions also occur within and outside of cells, are injurious, and have been implicated in a wide range of human diseases (see 13-Hydroxyoctadecadienoic acid, 9-hydroxyoctadecadienoic acid, reactive oxygen species, and Oxidative stress) as well as many of the maladies associated with ageing (see ageing).[25][26][27] Recent advances enable the use of radical intermediates in asymmetric radical reactions. High enantioselectivity during target bond formation is achieved by employing chiral organocatalysts, transition-metal redox catalysis, photoredox dual systems, or biocatalysts.[28]
See also
References
- ↑ Über die Darstellung von freiem Methyl Berichte der deutschen chemischen Gesellschaft (A and B Series) Volume 62, Issue 5, Pages 1335–47 Fritz Paneth, Wilhelm Hofeditz doi:10.1002/cber.19290620537
- ↑ Free Radical Reaction – from Eric Weisstein's World of Chemistry
- ↑ Template:JerryMarch
- ↑ 4.0 4.1 Advanced Organic Chemistry F.A. Carey R.J. Sundberg ISBN 0-306-41198-9 Search this book on
.
- ↑ Ansylen, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry. p. 573, ISBN 978-1-891389-31-3 Search this book on .
- ↑ March Jerry; (1985). Advanced organic chemistry reactions, mechanisms and structure (3rd ed.). New York: John Wiley & Sons, inc. ISBN 0-471-85472-7 Search this book on .
- ↑ "15.1: Free Radical Halogenation of Alkanes". Chemistry LibreTexts. 2015-01-05. Retrieved 2025-07-05.
- ↑ Simic, Michael G. (1981-02-01). "Free radical mechanisms in autoxidation processes". Journal of Chemical Education. 58 (2): 125. doi:10.1021/ed058p125. ISSN 0021-9584.
- ↑ McMurry, John; Emeritus, Professor (2023-09-20). "6.6 Radical Reactions - Organic Chemistry | OpenStax". openstax.org. Retrieved 2025-07-05.
- ↑ Wolff, Manfred E. (2002-05-01). "Cyclization of N-Halogenated Amines (The Hofmann-Löffler Reaction)". Chemical Reviews. 63: 55–64. doi:10.1021/cr60221a004. Retrieved 2025-07-05.
- ↑ Barton, Derek H. R.; Hesse, Robert H.; Pechet, Maurice M.; Smith, Leslie C. (1979-01-01). "The mechanism of the barton reaction". Journal of the Chemical Society, Perkin Transactions 1: 1159–1165. doi:10.1039/P19790001159. hdl:1893/35137. ISSN 1364-5463.
- ↑ 12.0 12.1 Ansylen, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry. p. 683, ISBN 978-1-891389-31-3 Search this book on .
- ↑ 13.0 13.1 "12.2: Radical Reactions". Chemistry LibreTexts. 2022-01-18. Retrieved 2025-07-05.
- ↑ Beckwith, A. L. J.; Ingold, K. U. (1980-01-01), de Mayo, Paul, ed., "Essay 4 - Free-Radical Rearrangements", Organic Chemistry: A Series of Monographs, Rearrangements in Ground and Excited States, Academic Press, 42, pp. 161–310, doi:10.1016/B978-0-12-481301-4.50010-3, retrieved 2025-07-05
- ↑ Chemistry (IUPAC), The International Union of Pure and Applied. "IUPAC - homolysis (H02851)". goldbook.iupac.org. doi:10.1351/goldbook.H02851. Retrieved 2025-07-05.
- ↑ Majhi, Sasadhar (2021-10-01). "Applications of Norrish type I and II reactions in the total synthesis of natural products: a review". Photochemical & Photobiological Sciences. 20 (10): 1357–1378. Bibcode:2021PhPhS..20.1357M. doi:10.1007/s43630-021-00100-3. ISSN 1474-9092. PMID 34537894 Check
|pmid=value (help). - ↑ Johnson, Robert G.; Ingham, Robert K. (1956-04-01). "The Degradation Of Carboxylic Acid Salts By Means Of Halogen - The Hunsdiecker Reaction". Chemical Reviews. 56 (2): 219–269. doi:10.1021/cr50008a002. ISSN 0009-2665.
- ↑ Li, Liubo; Yao, Yan; Fu, Niankai (2023). "Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization". European Journal of Organic Chemistry. 26 (21). doi:10.1002/ejoc.202300166. ISSN 1099-0690. Unknown parameter
|article-number=ignored (help) - ↑ Kochi, J. K. (1962-01-01). "The mechanism of the copper salt catalysed reactions of peroxides". Tetrahedron. 18 (4): 483–497. doi:10.1016/S0040-4020(01)92696-1. ISSN 0040-4020.
- ↑ Vijh, A. K.; Conway, B. E. (1967-12-01). "Electrode Kinetic Aspects of the Kolbe Reaction". Chemical Reviews. 67 (6): 623–664. doi:10.1021/cr60250a003. ISSN 0009-2665.
- ↑ Rossi, Roberto A. (1982-06-01). "Phenomenon of radical anion fragmentation in the course of aromatic SRN reactions". Accounts of Chemical Research. 15 (6): 164–170. doi:10.1021/ar00078a001. ISSN 0001-4842.
- ↑ Melikyan, Gagik G. (2004), "Carbon–Carbon Bond-Forming Reactions Promoted by Trivalent Manganese", Organic Reactions, John Wiley & Sons, Ltd, pp. 427–675, doi:10.1002/0471264180.or049.03, ISBN 978-0-471-26418-7, retrieved 2025-07-05
- ↑ Ansylen, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry. p. 596, ISBN 978-1-891389-31-3 Search this book on .
- ↑ Robert T. Morrison, Robert N. Boyd, and Robert K. Boyd, Organic Chemistry, 6th edition (Benjamin Cummings), 1992, ISBN 0-13-643669-2 Search this book on .
- ↑ Free Radic Biol Med. 2006 Aug 1;41(3):362–87
- ↑ Mol Biotechnol. 2007 Sep;37(1):5–12
- ↑ Biochim Biophys Acta. 2014 Feb;1840(2):809–17. doi: 10.1016/j.bbagen.2013.03.020
- ↑ Mondal, Shovan; Dumur, Frédéric; Gigmes, Didier; Sibi, Mukund P.; Bertrand, Michèle P.; Nechab, Malek (2022-03-23). "Enantioselective Radical Reactions Using Chiral Catalysts". Chemical Reviews. 122 (6): 5842–5976. doi:10.1021/acs.chemrev.1c00582. ISSN 0009-2665.
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