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The cyclization of 4,5-dihydroxy-2-methyl-pyrimidine followed by dibromination and oxidation of the methyl group led to 6,7-dihydro-[1,4]dioxino[2,3-d]pyrimidine-2-carboxaldehyde. This compound underwent different chemical transformations on carbonyl group to synthesize various 2-substituted-6,7- dihydro-[1,4]dioxino[2,3-d]pyrimidines.