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In current work, heteroannulation of 2‐amino‐6‐thioxouracil to new fused pyrimidine scaffolds is described, where pyrimidine 1 undergoes cyclocondensation with pyruvic acid derivative 2 and ninhydrin (6) to furnish thiopyranopyrimidine 5 and thienopyrimidine 8, respectively. Alkylation of aminopyrimidine 1 with benzyl chloride consumed two moles to form S‐ and N‐alkylated product 9. Subjecting compound...