Gomberg–Bachmann reaction

From Wikipedia, the free encyclopedia
  (Redirected from Gomberg-Bachmann reaction)
Jump to: navigation, search

The Gomberg–Bachmann reaction, named for the Ukrainian-American chemist Moses Gomberg and the American chemist Werner Emmanuel Bachmann, is an aryl-aryl coupling reaction via a diazonium salt.[1][2][3]

Gomberg-Bachmann reaction

The arene compound 1 (here benzene) is coupled with base with the diazonium salt 2 to the biaryl 3 through an intermediate aryl radical. For example, p-bromobiphenyl may be prepared from 4-bromoaniline and benzene:[4]

BrC6H4NH2 + C6H6 → BrC6H4−C6H5

The reaction offers a wide scope for both diazonium component and arene component but yields are generally low following the original procedure (less than 40%), given the many side-reactions of diazonium salts. Several improvements have been suggested. One possibility is to employ diazonium tetrafluoroborates in arene solvent together with a phase-transfer catalyst,[5] another is to use 1-aryl-3,3-dialkyltriazenes.[6]

Pschorr reaction[edit]

One intramolecular variation which gives better results is the Pschorr reaction:[7][8][9]

Pschorr reaction

The group Z can be CH2, CH2CH2, NH and CO (to fluorenone [10]) to name just a few.

See also[edit]

References[edit]

  1. ^ M. Gomberg, W. E. Bachmann (1924). J. Am. Chem. Soc. 42 (10): 2339–2343. doi:10.1021/ja01675a026. 
  2. ^ W. Pötsch. Lexikon bedeutender Chemiker (VEB Bibliographisches Institut Leipzig, 1989) (ISBN 3817110553)
  3. ^ M. B. Smith, J. March. March's Advanced Organic Chemistry (Wiley, 2001) (ISBN 0-471-58589-0)
  4. ^ M. Gomberg and W. E. Bachmann (1941), "p-Bromobiphenyl", Org. Synth. ; Coll. Vol. 1: 113 
  5. ^ J.R. Beadle, S.H. Korzeniowski, D.E. Rosenberg, B.J. Garcia-Slanga, G.W. Gokel (1984). "Phase-transfer-catalyzed Gomberg-Bachmann synthesis of unsymmetrical biarenes: a survey of catalysts and substrates". J. Org. Chem. 49 (9): 1594–603. doi:10.1021/jo00183a021. 
  6. ^ T.B. Patrick, R.P. Willaredt, D.J. DeGonia (1985). "Synthesis of biaryls from aryltriazenes". J. Org. Chem. 50 (13): 2232–2235. doi:10.1021/jo00213a007. 
  7. ^ R. Pschorr (1896). "Neue Synthese des Phenanthrens und seiner Derivate". Chem. Ber. 29: 496. doi:10.1002/cber.18960290198. 
  8. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley, ISBN 0-471-85472-7 
  9. ^ Review Article, Kenneth K. Laali and Mohammadreza Shokouhimehr, The Pschorr Reaction, a Fresh Look at a Classical Transformation Current Organic Synthesis, 2009, 6, 193–202. doi:10.2174/157017909788167275
  10. ^ Stephen A. Chandler, Peter Hanson, Alec B. Taylor, Paul H. Walton and Allan W. Timms (2001). "Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics". J. Chem. Soc., Perkin Trans. 2 (2): 214–228. doi:10.1039/b006184k.