A series of pyrano[2,3-d]pyrimidine derivatives were synthesized by the reaction of aromatic aldehyde, malononitrile and 2-amino-4,6-dihydroxylpyrimidine in the presence of benzyltrimethyl ammonium bromide in water at 80 degrees C. The structures of the products were characterized by IR, H-1 NMR spectra and elemental analysis. Compared with other synthetic methods, this method has the advantages of neutral conditions, high yields and simple work-up procedures. In addition, water as a green solvent gave some merits such as cheapness, safty, and non-pollution.