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Duff Reaction




The Electrophilic species in this Electrophilic Aromatic Substitution reaction is the Iminium ion CH2+NR2. The initial reaction product is an Iminium which is Hydrolyzed to the Aldehyde . See mechanism below. The reaction requires strongly Activating substituents on the aromatic ring such as in a Phenol .


REACTION MECHANISM

The Reaction Mechanism displayed below demonstrates step by step how hexamine donates a Methine group to an aromatic substrate via a series of equilibria reactions, with Iminium ion intermediates. Initially, addition to the aromatic ring results in an intermediate at the oxidation state of a benzylamine. An intramolecular redox reaction then ensues, raising the benzylic carbon to the oxidation state of an aldehyde. The oxygen atom is kindly provided by water on acid hydrolysis in the final step.


REFERENCES

  • Duff, J. C.; Bills, E. J. ''J. Chem. Soc.'' 1932, 1987.

  • Duff, J. C.; Bills, E. J. ''J. Chem. Soc.'' 1934, 1305.

  • Duff, J. C.; Bills, E. J. ''J. Chem. Soc.'' 1941, 547.

  • Duff, J. C.; Bills, E. J. ''J. Chem. Soc.'' 1945, 276.

  • Ferguson, L. N. ''Chem. Rev.'' 1946, ''38'', 227.

  • Ogata, Y.; Sugiura, F. ''Tetrahedron'' 1968, ''24'', 5001.

  • 3,5-Di-tert-butylsalicylaldehyde in Organic Syntheses Coll. Vol. 10, p.96; Vol. 75, p.1 ( Article )

  • Syringaldehyde in Organic Syntheses Coll. Vol. 4, p.866; Vol. 31, p.92 ( Article )



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