Demjanov rearrangement

What is Demjanov rearrangement?

The Demjanov rearrangement, also known as the Demjanov reaction, is a chemical process discovered by Demjanov in 1903, which converts primary amines into alcohols using nitrous acid for diazotization. The reaction causes the migration of the carbon atom when the primary amino groups are present on the ring or at the α-position of the side chain.

Demjanov rearrangement
Demjanov rearrangement

The reaction can result in either ring enlargement or contraction, depending on the position of the amino group in the case of cyclic aliphatic amines. Ring contraction occurs when the amino group is directly attached to the ring, while ring expansion occurs when the amino group is connected to the cyclic ring via a methylene group. The Demjanov rearrangement is also referred to as the Demjanov ring expansion under this condition. In the presence of an aminomethylene group in the same position as an aromatic group, the reaction leads to phenyl migration without ring enlargement.

Overall, the Demjanov rearrangement is a chemical reaction that involves the deamination of primary amines through diazotization, leading to the formation of rearranged alcohols. The reaction is named after its discoverer, Demjanov, and is also known as the Demjanov reaction. The reaction causes either ring enlargement or contraction, especially in the case of alicyclic amines, depending on the position of the amino group.

References

  • Demjanov, N.J.; Luschnikov, M.;  J. Russ. Phys. Chem. Soc. 33: 279-283 (1901)
  • Demjanov, N.J.; Lushnikov, M.; J. Russ. Phys. Chem. Soc. 35: 26-42 (1903)
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