McFadyen–Stevens reaction
Appearance
The McFadyen–Stevens reaction is a chemical reaction best described as a base-catalyzed thermal decomposition of acylsulfonylhydrazides to aldehydes.[1][2]
![The McFadyen–Stevens reaction](http://upload.wikimedia.org/wikipedia/commons/thumb/3/3a/McFadyen-Stevens_Reaction_Scheme.png/350px-McFadyen-Stevens_Reaction_Scheme.png)
Dudman et al. have developed an alternative hydrazide reagent.[3]
Reaction mechanism
[edit]The mechanism of the McFadyen–Stevens reaction is still under investigation. Two groups have independently proposed a heterolytic fragmentation mechanism.[4][5] The mechanism involves the deprotonation of the acyl sulfonamide followed by a 1,2-hydride migration to give the alkoxide (3). The collapse of the alkoxide results in the fragmentation producing the desired aldehyde (4), nitrogen gas, and an aryl sulfinate ion (5).
![The mechanism of the McFadyen–Stevens reaction](http://upload.wikimedia.org/wikipedia/commons/thumb/3/36/McFadyen-Stevens_Reaction_Mechanism.png/650px-McFadyen-Stevens_Reaction_Mechanism.png)
Martin et al. have proposed a different mechanism involving an acyl nitrene.[6]
See also
[edit]References
[edit]- ^ McFadyen, J. S.; Stevens, T. S. (1936). "128. A new method for the conversion of acids into aldehydes". J. Chem. Soc.: 584. doi:10.1039/jr9360000584.
- ^ Mosettig, E. (1954). "The Synthesis of Aldehydes from Carboxylic Acids". Org. React. Vol. 8. pp. 232–240. doi:10.1002/0471264180.or008.05. ISBN 0471264180.
- ^ Dudman, C. C.; Grice, Peter; Reese, Colin B.; et al. (1980). "Use of 2,4,6-tri-isopropylbenzenesulphonyl hydrazide in the mcfadyen-stevens aldehyde synthesis". Tetrahedron Lett. 21 (48): 4645. doi:10.1016/0040-4039(80)80096-7.
- ^ Brown, V. M.; Carter, P. H.; Tomlinson, M. (1958). "374. Formyl compounds. Part II". J. Chem. Soc.: 1843. doi:10.1039/jr9580001843.
- ^ Campaigne, E.; Thompson, R. L.; Van Werth, J. E. (1959). "Some Heterocyclic Aldehyde Thiosemicarbazones Possing Anti-viral Activity". J. Med. Chem. 1 (6): 577–599. doi:10.1021/jm50007a003. PMID 13807198.
- ^ Martin, S. B.; Craig, J. C.; Chan, R. P. K. (1974). "An Investigation of the McFadyen-Stevens Reaction". The Journal of Organic Chemistry. 39 (15): 2285. doi:10.1021/jo00929a600.