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Allan–Robinson reaction

From Wikipedia, the free encyclopedia
Chemical reaction

TheAllan–Robinson reaction is thechemical reaction of o-hydroxyarylketones with aromaticanhydrides to formflavones (orisoflavones).[1][2][3][4]

Ifaliphatic anhydrides are used,coumarins can also be formed. (SeeKostanecki acylation.)

Reaction overview

Mechanism

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The o-hydroxyaryl ketone first undergoestautomerization to form the respectiveenol. Thepi electrons of thedouble bond then attack the electrophilic carbon of the anhydride; acarboxylate anion is subsequently lost as a leaving group. The carboxylate anion then attacks an alpha hydrogen to form an enol. The nucleophilic hydroxyl group then attacks the carbonyl carbon to form a six-memberedheterocyclic ring. A proton is abstracted from the hydroxyl group of the enol to form a ketone, and the remaining hydroxyl group is lost as a leaving group in a concerted step to afford the final product.[4][5]

See also

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References

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  1. ^Allan, J.; Robinson, R.J. Chem. Soc.1924,125, 2192.
  2. ^Dyke, S. F.; Ollis, W. D.; Sainsbury, M.J. Org. Chem.1961,26, 2453. (doi:10.1021/jo01351a072)
  3. ^Wheller, T. S. (1952)."Flavone".Organic Syntheses.32: 72.doi:10.15227/orgsyn.032.0072.
  4. ^abJie Jack Li (2009).Name Reactions. A Collection of Detailed Reaction Mechanisms 4th Edition. Berlin, De: Springer.ISBN 978-3-642-01052-1.
  5. ^Graham, Solomons, T. W. (17 January 2013).Organic chemistry. Fryhle, Craig B.,, Snyder, S. A. (Scott A.) (11e ed.). Hoboken, NJ.ISBN 9781118147399.OCLC 820665397.{{cite book}}: CS1 maint: location missing publisher (link) CS1 maint: multiple names: authors list (link)
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