Английская Википедия:Blaise ketone synthesis

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Шаблон:Reactionbox The Blaise ketone synthesis (named after Edmond Blaise) is the chemical reaction of acid chlorides with organozinc compounds to give ketones.Шаблон:RefШаблон:Ref

The Blaise ketone synthesis
The Blaise ketone synthesis

The reaction was claimed to bring excellent yields by Blaise, however, investigators failed to obtain better than moderate yields (50%).Шаблон:RefШаблон:Ref Thus, the reaction is particularly ineffective in forming ketones from acyl chlorides. The reaction also works with organocuprates.Шаблон:RefШаблон:Ref Reviews have been written.Шаблон:RefШаблон:Ref

Reaction mechanism

The mechanism is sampled from the proposed mechanism for organocadmium compounds, given that the mechanisms are identical to one another the proposed mechanism for the reaction is the same as the one for organocadmium compoundsШаблон:RefШаблон:Ref.

Proposed mechanism for the Blaise ketone synthesis.
Proposed mechanism for the Blaise ketone synthesis.

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.Шаблон:Ref

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.Шаблон:Ref

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

Шаблон:Reflist

  1. Шаблон:Note Шаблон:Cite journal
  2. Шаблон:Note Шаблон:Cite journal
  3. Шаблон:Note Шаблон:OrgSynth
  4. Шаблон:Note Шаблон:OrgSynth
  5. Шаблон:Note Шаблон:Cite journal
  6. Шаблон:Note Шаблон:Cite journal
  7. Шаблон:Note Шаблон:Cite journal
  8. Шаблон:Note Шаблон:Cite journal
  9. Шаблон:Note Шаблон:Cite book

Шаблон:Organic reactions Шаблон:Reaction-stub