The catalytic efficiency of ammonium dihydrogen phosphate for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones was studied with various amount of NH4H2PO4 (Table 1). To determine the role of the catalyst, a blank reaction of 4-nitrobenzaldehyde, ethyl acetoacetate, and urea was carried out in the absence of catalyst. The reaction did not give the desired product efficiently in the absence of catalyst, and it gave many impurity byproducts after an extended time of 8 h (entry 1). The presence of the catalyst, only 0.5 mol% of NH4H2PO4, gave 47% conversion after 3 h (entry 2), which showed that the catalyst has high catalytic activity. Table 1 shows that increasing catalyst amount initially led to high yield at short reaction time. However, 5 mol% of the catalyst was enough for the reaction. With more catalyst (10 mol%), the yield progressed very smoothly to 93% without decreasing the reaction time (entry 5). Even more catalyst (>10 mol%) not only failed to improve the yield, but also decreased the efficiency of the catalytic system (Fig. 1). This behavior was explained by the changes in polarity, pH, and components of the reaction mixture in the solvent-free system. Thus, 5 mol% of NH4H2PO4 was selected for all the reactions.