The first example of the Fischer–Hepp type rearrangement in pyrimidines

• Inga Cikotiene,
• Mantas Jonusis and
• Virginija Jakubkiene

Beilstein J. Org. Chem. 2013, 9, 1819–1825, doi:10.3762/bjoc.9.212

• -pyrimidinediamines. It was found that the outcome of the reaction strongly depends on the structure of the pyrimidines. Activation of the pyrimidine ring by three groups with a positive mesomeric effect is crucial for the intramolecular nitroso group migration. Keywords: Fischer–Hepp rearrangement; nitrosation; 5

• presence of a group with a positive mesomeric effect in position 2 of the pirimidine ring is crucial for the migration of the nitroso group to C-5. The migration of a nitroso group in benzene derivatives is a well-known reaction, named Fischer–Hepp rearrangement (Scheme 5) [40][41][42]. The classical

• Fischer–Hepp rearrangement takes place when N-nitroso secondary anilines are treated with HCl or HBr, other acids give poor results or none at all. To the best of our knowledge, there are no examples of the migration of a nitroso group in heterocyclic compounds in the scientific literature. Obviously, the