Duff reaction

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The Duff reaction is a name reaction in organic chemistry and named after James Cooper Duff . The reaction is used to introduce a formyl group  (-CHO) into aromatic hydrocarbons . In this reaction, hexamethylenetetramine serves as the source of the carbonyl group to be introduced. The reaction is favored by activated aromatics such as phenol or N , N -dialkylanilines.

Mechanism of the Duff reaction

Examples

The formylation takes place preferably in the ortho position to the electron donor substituent. If the ortho position is occupied, the formylation takes place in the para position. An example is the synthesis of 3,5-di- tert -butylsalicylaldehyde:

Example 1 Duff reaction

And the synthesis of syringaldehyde :

Example 2 Duff reaction

Individual evidence

  1. ^ Z. Wang: Comprehensive Organic Name Reactions and Reagents. 3-Volume Set Volume 1, Wiley, 2009, ISBN 978-0-471-70450-8 , pp. 942-945.
  2. ↑ Bradford P. Mundy, Michael G. Ellerd, Frank G. Favaloro: Name Reactions and Reagents in Organic Synthesis. 2nd ed., John Wiley & Sons, 2005, pp. 222-223.
  3. ↑ Jay F. Larrow, Eric N. Jacobsen: (R, R) -N, N'-Bis (3,5-di-tert-Butylsalicylidene) -1,2-Cyclohexanediamino Manganese (III) Chloride, A Highly Enantioselective Epoxidation Catalyst Template: link text check / apostrophe In: Organic Syntheses . 75, 1998, p. 1, doi : 10.15227 / orgsyn.075.0001 ( PDF ).
  4. ↑ CFH Allen, Gerhard W. Leubner: Syringic Aldehyde In: Organic Syntheses . 31, 1951, p. 92, doi : 10.15227 / orgsyn.031.0092 ; Coll. Vol. 4, 1963, p. 866 ( PDF ).

literature

  • JC Duff, EJ Bills: Reactions between hexamethylenetetramine and phenolic compounds. Part I. A new method for the preparation of 3- and 5-aldehydosalicylic acids. In: Journal of the Chemical Society (Resumed). 1932, pp. 1987-1988, doi : 10.1039 / JR9320001987 .
  • JC Duff, EJ Bills: Reactions between hexamethylenetetramine and phenolic compounds. Part II. Formation of phenolic aldehydes. Distinctive behavior of p-nitrophenol. In: Journal of the Chemical Society (Resumed). 1934, pp. 1305-1308, doi : 10.1039 / JR9340001305 .
  • James C. Duff: A new general method for the preparation of o-hydroxyaldehydes from phenols and hexamethylenetetramine. In: Journal of the Chemical Society (Resumed). 1941, pp. 547-550, doi : 10.1039 / JR9410000547 .
  • James C. Duff: A new method for the preparation of p-dialkylaminobenzaldehydes. In: Journal of the Chemical Society (Resumed). 1945, pp. 276-277, doi : 10.1039 / JR9450000276 .
  • Lloyd N. Ferguson: The Synthesis of Aromatic Aldehydes. In: Chemical Reviews. 38, No. 2, 1946, pp. 227-254, doi : 10.1021 / cr60120a002 .
  • Y. Ogata, A. Kawasaki, F. Sugiura: Kinetics and mechanism of the Duff reaction. In: Tetrahedron. 24, No. 14, 1968, pp. 5001-5010, doi : 10.1016 / S0040-4020 (01) 88408-8 .