Synthetic routes to the unsubstituted 4H-thiopyran-Cone 1, l-dioxide (5a), 2, 6-dialkyl- substituted, 2-aryl-or 2-heteroaryl-6-alkyl-substituted, 2, 6-diaryl-or diheteroaryl-substituted, and 2-heteroaryl-6-aryl-substituted 4H-thiopyran-4-one 1, l-dioxides 5b-s are described. Sodium hydrosulfide hydrate in buffered aqueous alcohol can be used as a substitute for hydrogen sulfide gas for the introduction of sulfur to methyl acrylate, to 1, 5-disubstituted-l, ...