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Reactions of β-1,2,3-thiadiazol-5-yl enamines with acetyl chloride in 1,4-dioxane lead to the formation of either dienamines or novel thieno[2,3-d]pyridazines depending on the time and reaction temperature. Conditions were found for the selective synthesis of thieno[2,3-d]pyridazines. A plausible mechanism involves formation of C–S and C–C bonds and a novel ring rearrangement of 5-vinyl-1,2,3-thiadiazoles...