Delepine reaction

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The Delépine Reaction or Delepine reaction is the organic synthesis of primary amines (4) by acid hydrolysis of a quaternary hexamethylenetetramine salt (3), obtained from alkylation of hexamethylenetetramine (2) with benzyl or alkyl halides (1) M. Delépine: Bull.Soc.Chim.Fr.. 1895, 13, S. 352 - 361 Alexander R. Surrey: Name Reactions in Organic Chemistry. 2nd Edition, Academic Press, 1961.

Advantages of this reaction are selective access to the primary amine without side reactions from easily accessible reactants with short reaction times and relatively mild reaction conditions.

An example is the synthesis of 2-bromoallylamine from 2,3-dibromopropene 2-bromoallylamine Albert T. Bottini, Vasu Dev, and Jane Klinck Organic Syntheses, Coll. Vol. 5, p.121 (1973); Vol. 43, p.6 (1963)..

Reaction mechanism

The benzyl halide or alkyl halide 1 reacts with hexamethylenetetramine to a quaternary ammonium salt 3, each time just alkylating one nitrogen atom. By refluxing in concentrated ethanolic hydrochloric acid solution this salt is converted to the primary amine together with formaldehyde (as the acetal with ethanol) and ammonium chloride.

References

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