The Tishchenko reaction is an organic chemical reaction that involves disproportionation of an aldehyde lacking a hydrogen atom in the alpha position in the presence of an alkoxide. The reaction product is an ester. Catalysts are aluminium alkoxides or sodium alkoxides.
- Benzaldehyde reacts with sodium benzyloxide (generated from sodium and benzyl alcohol) to benzyl benzoate.
- The Tishchenko reaction of acetaldehyde gives the commercially important solvent ethyl acetate; it is catalyzed by aluminium alcoholate.
- Hydroxypivalic acid neopentyl glycol ester is produced by a Tishchenko reaction from hydroxypivaldehyde in the presence of a basic catalyst (e.g., aluminium oxide).
- The Tishchenko reaction of paraformaldehyde in the presence of aluminum methylate or magnesium methylate forms methyl formate.
- Paraformaldehyde reacts with boric acid to form methyl formate. The key step in the reaction mechanism for this reaction is a 1,3-hydride shift in the hemiacetal intermediate formed from two successive nucleophilic addition reactions, the first one from the catalyst. The hydride shift regenerates the alkoxide catalyst.
- Aldol–Tishchenko reaction
- Baylis–Hillman reaction
- Cannizzaro reaction
- Meerwein–Ponndorf–Verley reduction
- Oppenauer oxidation
- V. Tishchenko (1908), J. Russ. Phys. Chem. Soc 38: 355, 482
- Kamm, O.; Kamm, W. F. (1941), "Benzyl benzoate", Org. Synth.; Coll. Vol. 1: 104
- Marc Eckert, Gerald Fleischmann, Reinhard Jira, Hermann M. Bolt, Klaus Golka (2007), "Acetaldehyde", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 4
- Boy Cornils, Richard W. Fischer, Christian Kohlpaintner (2007), "Butanals", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 4
- Peter Werle, Marcus Morawietz (2007), "Alcohols, Polyhydric", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 6
- Günther Reuss, Walter Disteldorf, Armin Otto Gamer, Albrecht Hilt (2007), "Formaldehyde", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 5
- Paul R. Stapp (1973). "Boric acid catalyzed Tishchenko reactions". J. Org. Chem. 38 (7): 1433–1434. doi:10.1021/jo00947a049.