Abstract 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 H 2 SO 4 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 ...