Chalcogenopyranones from Disodium Chalcogenide Additions to 1,4-Pentadiyn-3-ones. The Role of Enol Ethers as Intermediates

摘要

Enol ethers 9 are formed as a mixture of E- and Z-isomere from the addition of ethanol to 1,4-pentadiyn-3-ones 2 in sodium ethoxide/ethanol. The enol ethers react with disodium chalcogenides to give the corresponding 2,6-disubstituted chalcogenopyranones 1 bearing alkyl, aryl, or heteroaryl substituents in high yield as the only heterocyclic product of reaction. Diynones 2 react with disodium chalcogenides to give mixtures of products in which the chalcogenopyranones 1 are minor components and the dihydrochalcogenophenes 3 are the major products. The addition of hydrogen sulfide to diynone 2b in ethanol gives a product mixture nearly identical to that observed for the addition of disodium sulfide in sodium ethoxide in ethanol to 2b. Intermediates for the addition of hydrogen chalcogenides and disodium chalcogenides to both 2 and 9 are described, which lead to the heterocyclic products.