Bouveault aldehyde synthesis

Bouveault Aldehyde Synthesis

The reaction for synthesis of aldehydes by the treatment of N, N-disubstituted formamides with either Grignard reagent or organic lithium reagent in an ether solvent is generally known as Bouveault aldehyde synthesis or you in a simple way it is a one-pot chemical reaction that converts a primary alkyl halide to an aldehyde one carbon longer.  This reaction has been reported to work only in certain cases and occasionally this reaction produces tertiary amines as the main products. The study finds that the greater the R group in the Grignard reagent, the more aldehyde is yielded. This reaction has been improved by either running in a co-solvent of ether-HMPA or irradiating with high-frequency ultrasound in THF or tetahydropyran. This reaction has general application in the preparation of aldehydes.

Reaction mechanism

  

The first step of the Bouveault aldehyde synthesis is the formation of the Grignard reagent. Upon addition of a N,N-disubstituted formamide (such as DMF) a hemiaminal is formed, which can easily be hydrolyzed into the desired aldehyde .

Literature

• 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).
• Smith, L. I.; Nichols, J. (1941). "The Synthesis of Aldehydes from Grignard Reagents. II. Polymethylbenzaldehydes". J. Org. Chem. 6 (4): 489.
• Sice, Jean (1953). "Preparation and Reactions of 2-Methoxythiophene". J. Am. Chem. Soc. 75 (15): 3697.
• Comins, D.L.; Brown, J.D. J. Org. Chem. 1984, 49, 1078 (region selective control)
• Meier, H.; Aust, H. J. Prakt. Chem. 1999, 341, 466 (uses DMA for ketone and DMF for aldehyde synthesis)
• L. Bouveault, Bull. Soc. Chim. France 31, 1306, 1322 (1904).