Base-catalyzed trimerization of N-cyanomethylazoles under pressure and in solvent-free conditions afforded 4-amino-2, 6-bis (azol-1-ylmethyl)-5-(azol-1-yl) pyrimidines (1–3) in 33– 67% yields. The structures of these compounds was determined by a combination of NMR techniques and X-ray crystallography. The 4-amino groups show a restricted rotation around the C–N bond; the free energy of activation for this process was determined by variable ...