A new synthesis of 2-substituted-4H-chromen-4-ones (IVa-c) and 4-(2-hydroxyphenyl)-6-substituted pyrimidin- 2(5H)-one/thiones (Va - Vc)/(VIa - VIc) derivatives is reported. First, benzoyloxy esters are converted into their 1,3-diones (IIIa - IIIc) by using dry KOH in pyridine via the Baker - Venkataraman transformation reaction. Then, 1,3-diones thus obtained are cyclised into 2-substituted-4H-chromen-4-ones (IVa - IVc) and 4-(2-hydroxyphenyl)-6-substituted pyrimidin-2(5H)-one/thiones (Va - Vc)/(VIa - VIc) by refluxing in acetic acid and urea/thiourea in ethanol, respectively. The newly synthesized compounds were characterized by IR, H-1 NMR, and mass spectroscopy and elemental analysis and tested for their antibacterial and antifungal activity.