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Saturday, 22 October 2011

Bodroux-Chichibabin aldehyde synthesis

Bodroux-Chichibabin aldehyde synthesis

The Bodroux-Chichibabin aldehyde synthesis is a chemical reaction whereby a Grignard reagent is converted to an aldehyde one carbon longer.

This synthesis involves the treatment of ethyl orthoformate with corresponding Grignard reagents to form of aliphatic or aromatic aldehydes is generally referred to as Bodroux-Chichibabin reaction. Other orthoformates have also been used for this reaction. When ethyl orthoformate is applied in this reaction, the replacement of the first ethoxyl group is a slow reaction, but the yields can be improved by refluxing the mixture of Grignard reagent and orthoformate. The yields of the reaction have been improved by refluxing the mixture of Grignard reagent and orthoformate. In this reaction the acetals with axial 2-alkoxy groups react rapidly with a variety of Grignard reagents.

Reaction of a Grignard reagent with triethyl orthoformate gives an acetal, which can be hydrolyzed to an aldehyde.


Mechanism

Nucleophillic attack by the Grignard on the electrophillic triacetal is followed by acid catalyzed hydrolysis of the diacetal to give the aldehyde.

Literature
  • F. Bodroux, Compt. Rend. 138, 92 (1904)
  • E. Chichibabin, Ber. 37, 186, 850 (1904)
  • F. Bohlmann, Ber. 86, 63, 657 (1933)
  • L. I. Smith et al., J. Org. Chem. 6, 437, 489 (1941)
  • H. W. Post, The Chemistry of the Aliphatic Orthoesters, p 96 (New York, 1943)
  • E. H. Rodd, Chemistry of Carbon Compounds 1, 614 (New York, 1951)
  • O. Bayer, Houben- Weyl-Muller 7 65 (1951)
  • L. I. Smith, J. Nichols, J. Org. Chem. 6, 489 (1941)
  • J. Sicé J. Am. Chem. Soc. 75, 3697 (1953)
  • E. R. H. Jones et al., J. Chem. Soc. 1958, 1054
  • Use of lithio derivatives instead of Grignard reagents: E. A. Evans, Chem. & Ind. (London) 1957, 1596
  • Synthetic applications using modified conditions: C. Pétrier et al., Tetrahedron Letters 23, 3361 (1982).
  • J. Einhorn, J. L. Luche, ibid. 27, 1791 (1986)
  • H. Meier, H. Aust, J. Prakt. Chem. 341, 466 (1999)


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