Wurtz–Fittig reaction
Named after Charles Adolphe Wurtz
Wilhelm Rudolph Fittig
Reaction type Coupling reaction
Identifiers
Organic Chemistry Portal wurtz-fittig-reaction

The Wurtz–Fittig reaction is the chemical reaction of an aryl halide, alkyl halides, and sodium metal to give substituted aromatic compounds.[1] Following the work of Charles Adolphe Wurtz on the sodium-induced coupling of alkyl halides (the Wurtz reaction), Wilhelm Rudolph Fittig extended the approach to the coupling of an alkyl halide with an aryl halide.[2][3] This modification of the Wurtz reaction is considered a separate process and is named for both scientists.[1]

The Wurtz–Fittig reaction

The reaction works best for forming asymmetrical products if the halide reactants are somehow separate in their relative chemical reactivities. One way to accomplish this is to form the reactants with halogens of different periods. Typically the alkyl halide is made more reactive than the aryl halide, increasing the probability that the alkyl halide will form the organosodium bond first and thus act more effectively as a nucleophile toward the aryl halide.[4] Typically the reaction is used for the alkylation of aryl halides. With the use of ultrasound sodium reacts with some aryl halides to produce biphenyl compounds.[5]

Mechanism

The mechanism of the Wurtz–Fittig reaction has not been the subject of modern investigations. The process was once proposed to involve the combination of an alkyl and aryl radicals.[6][7] Another mechanistic proposal invoked the generation of organosodium intermediates.[8] The reaction of sodium and chlorobenzene produces triphenylene, which supports a role for radicals.[8] A role for organosodium compounds is supported by indirect evidence.[7][6] For example, addition of carbon dioxide to a mixture of sodium and isobutyl bromide results in the formation of 3-methylbutanoic acid after acid workup. [9][10]

Use of other metals

The Wurtz–Fittig reaction can be conducted using metals other than sodium. Some examples include potassium, iron, copper, and lithium.[11] When lithium is used, the reaction occurs with appreciable yield only under ultrasound.[12] Ultrasound is known to cleave halogen atoms from aryl and alkyl halides through a free-radical mechanism[13]

Applications

The Wurtz–Fittig reaction has limited applicability, because it is plagued by side reactions including rearrangements and eliminations.[11] The reaction has been applied to the laboratory synthesis of some organosilicon compounds.[14] One example is the conversion of tetraethyl orthosilicate to the mono-tert-butoxy derivative in 40% yield as summarized in this idealized equation:[15]

Si(OC2H5)4 + 2 Na + (CH3)3CCl → Si(OC2H5)3OC(CH3)3 + NaCl + C2H5ONa

Molten sodium was used.

Other organosilicon compounds synthesized using the Wurtz–Fittig reaction include silylated calixarenes[16] and vinylsilanes.[17]

See also

References

  1. 1 2 Wang, Zerong (2010). "Wurtz–Fittig Reaction". Comprehensive Organic Name Reactions and Reagents. Vol. 686. pp. 3100–3104. doi:10.1002/9780470638859.conrr686. ISBN 9780470638859.
  2. ↑ Tollens, Bernhard; Rudolph Fittig (1864). "Ueber die Synthese der Kohlenwasserstoffe der Benzolreihe" [On the synthesis of the hydrocarbons of the benzene series]. Justus Liebigs Annalen der Chemie (in German). 131 (3): 303–323. doi:10.1002/jlac.18641310307.
  3. ↑ Fittig, Rudolph; König, Joseph (1867). "Ueber das Aethyl- und Diäthylbenzol" [About ethyl- and diethylbenzene]. Justus Liebigs Annalen der Chemie (in German). 144 (3): 277–294. doi:10.1002/jlac.18671440308.
  4. ↑ Desai, K. R. (2008). Organic Name Reactions. Jaipur, India: Oxford Book Company. p. https://archive.org/details/handbookinorgani00desa/page/n267 259]. ISBN 9788189473327.
  5. ↑ Laue, Thomas; Plagens, Andreas (2005). Named Organic Reactions (2nd ed.). Wolfsburg, Germany: John Wiley & Sons. p. 305. ISBN 9780470010402.
  6. 1 2 Wooster, Charles Bushnell (1932). "Organo-alkali Compounds". Chemical Reviews. 11 (1): 1–91. doi:10.1021/cr60038a001. ISSN 0009-2665.
  7. 1 2 Gilman, Henry; Wright, George F. (1933). "The Mechanism of the Wurtz—Fittig Reaction. The Direct Preparation of an Organosodium (Potassium) Compound from an RX Compound". Journal of the American Chemical Society. 55 (7): 2893–2896. doi:10.1021/ja01334a044. ISSN 0002-7863.
  8. 1 2 Bachmann, W. E.; Clarke, H. T. (1927). "The Mechanism of the Wurtz–Fittig Reaction". Journal of the American Chemical Society. 49 (8): 2089–2098. doi:10.1021/ja01407a038. ISSN 0002-7863.
  9. ↑ Schorigin, Paul (1908). "Synthesen mittels Natrium und Halogenalkylen". Berichte der Deutschen Chemischen Gesellschaft. 41 (2): 2711–2717. doi:10.1002/cber.190804102208.
  10. ↑ Schorigin, Paul (1910). "Über die Natriumalkyle und über ihre Reaktion mit den Äthern". Berichte der Deutschen Chemischen Gesellschaft. 43 (2): 1931–1938. doi:10.1002/cber.191004302128.
  11. 1 2 Smith, Michael; March, Jerry (2007). March's advanced organic chemistry: Reactions, mechanisms, and structure (6th ed.). Hoboken, N.J.: Wiley-Interscience. ISBN 978-0471720911. OCLC 69020965.
  12. ↑ Han, Byung Hee; Boudjouk, Philip (1981). "Organic sonochemistry. Ultrasound-promoted coupling of organic halides in the presence of lithium wire". Tetrahedron Letters. 22 (29): 2757–2758. doi:10.1016/S0040-4039(01)90544-1. ISSN 0040-4039.
  13. ↑ Prakash, S.; Pandey, J. D. (1965). "Sonocleavage of halogens from aliphatic chains and aromatic rings". Tetrahedron. 21 (4): 903–908. doi:10.1016/0040-4020(65)80026-6. ISSN 0040-4020.
  14. ↑ Bassett, E. A.; Emblem, H. G.; Frankel, M.; Ridge, D. (1948). "The use of the Wurtz–Fittig reaction in the preparation of organo-substituted silanes". Journal of the Society of Chemical Industry. 67 (5): 177–179. doi:10.1002/jctb.5000670503. ISSN 0368-4075.
  15. ↑ Chappelow, C. C.; Elliott, R. L.; Goodwin, J. T. (1962). "Synthesis of t-Butylsilicon Compounds by the Wurtz–Fitting Reaction". The Journal of Organic Chemistry. 27 (4): 1409–1414. doi:10.1021/jo01051a069. ISSN 0022-3263.
  16. ↑ Hudrlik, Paul F.; Arasho, Wondwossen D.; Hudrlik, Anne M. (2007). "The Wurtz–Fittig Reaction in the Preparation of C-Silylated Calixarenes". The Journal of Organic Chemistry. 72 (21): 8107–8110. doi:10.1021/jo070660n. ISSN 0022-3263. PMID 17850095.
  17. ↑ Adam, Waldemar; Richter, Markus J. (1994). "One-Pot Synthesis of α-Trimethylsilyl Enones from Vinylsilanes". Synthesis. 1994 (2): 176–180. doi:10.1055/s-1994-25433. ISSN 0039-7881.
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