Blaise ketone synthesis
Blaise ketone synthesis | |
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Named after | Edmond Blaise |
Reaction type | Coupling reaction |
The Blaise ketone synthesis (named after Edmond Blaise) is the
The reaction was claimed to bring excellent yields by Blaise, however, investigators failed to obtain better than moderate yields (50%).[3][4] Thus, the reaction is particularly ineffective in forming ketones from acyl chlorides. The reaction also works with
Reaction mechanism
The mechanism is sampled from the proposed mechanism for
After the oxygen forms a bond with the organozinc compound, R’ shifts to the carbonyl carbon, having chlorine act as a leaving group and removing the negative charge from zinc. The chlorine that left returns to form a bond with zinc, pushing the electrons back on to oxygen and thus forming the ketone.[11]
Variations
Blaise-Maire reaction
The Blaise-Maire reaction is the Blaise ketone synthesis using β-hydroxy acid chlorides to give β-hydroxyketones, which are converted into α,β-unsaturated ketones using sulfuric acid.[12]
Ketone formation from organocadmium compounds
This ketone formation is an identical reaction to the Blaise ketone synthesis. Only instead of organozinc compounds, organocadmium compounds are used and produce higher yields.
See also
References
- Bull. Soc. Chim. Fr.7: 215–227.
- Bull. Soc. Chim. Fr.9: 1.
- ^ Posner, G. H.; Whitten, C. E. (1976). "Secondary and Tertiary Alkyl Ketones from Carboxylic Acid Chlorides and Lithium Phenylthio(Alkyl)Cuprate Reagents: tert-Butyl Phenyl Ketone". Organic Syntheses. 55: 122; Collected Volumes, vol. 6, p. 248.
- ^ Fujisawa, T.; Sato, T. (1988). "Ketones from Carboxylic Acids and Grignard Reagents: Methyl 6-Oxodecanoate". Organic Syntheses. 66: 116; Collected Volumes, vol. 8, p. 441.
- PMID 20287882.
- ISBN 0471264180.
- Compt. Rend.145: 73-75.
- .
- ISBN 0-582-46236-3.
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