Amination of 4,6- and 2,4-dichloropyrimidines with polyamines

Amination of a double excess of 4,6-dichloropyrimidine with various diamines in the presence of cesium carbonate in boiling dioxane quantitatively afforded the corresponding N,N′-bis(6-chloropyrimidin-4-yl) derivatives, while its reactions with tri- and tetraamines gave N,N′,N″-tris- and N,N′,N″,N‴-tetrakis(6-chloropyrimidin-4-yl) derivatives. Equimolar amounts of 2,4-dichloro- or 4,6-dichloropyrimidine and diamines reacted in the presence of Pd(0) complexes to form macrocyclic compounds containing pyrimidine fragments. Catalytic reactions of 4 equiv of diamines with 4,6-dichloropyrimidine can lead to the formation of 4,6-bis-(diamino)pyrimidines. Relations between the yield and the nature of diamine and catalytic system were found.