Abstract The reaction of N-(pyridin-3-yl) and-4-yl thiourea derivatives with malonyl dichloride in trifluoroacetic acid is shown to be an efficient synthesis of the corresponding thiobarbituric acids. The pyridin-2-yl analogue cleaved and produced, instead, 2-hydroxy-4H-pyrido [1, 2a] pyrimidin-4-one.