The first example of the Fischer-Hepp type rearrangement in pyrimidines.
A N-nitroso moiety can be used for the activation of chloropyrimidines toward a nucleophilic substitution reaction with amines. The subsequent treatment of the obtained products with aq H2SO4 can lead to either N-denitrosation to obtain 4,6-pyrimidinediamines or to a Fischer-Hepp type rearrangement to obtain 5-nitroso-4,6-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.
Department of Organic Chemistry, Faculty of Chemistry, Vilnius University, Naugarduko 24, LT-03225, Vilnius, Lithuania, Email: Inga Cikotiene - inga.cikotiene@chf.vu.lt.
Inga
I
Cikotiene
Mantas
M
Jonusis
Virginija
V
Jakubkiene
5-nitrosopyrimidines; Fischer–Hepp rearrangement; nitrosation; nucleophilic substitution; pyrimidinediamines