10.1002/jhet.5570360322
The research focuses on the synthesis of 4H-chalcogenopyran-4-ones using disodium chalcogenides and enol ethers derived from 1,4-pentadiyn-3-ones. Key chemicals involved include diynones such as 1,5-diphenyl-1,4-pentadiyn-3-one (2a), 1,5-di-tert-butyl-1,4-pentadiyn-3-one (2b), and 1,5-di-(4-N,N-dimethylaminophenyl)-1,4-pentadiyn-3-one (2c), which are reacted with disodium chalcogenides like disodium sulfide, disodium selenide, and disodium telluride. Enol ethers 9 are formed as intermediates from the addition of ethanol to diynones in sodium ethoxide/ethanol, and these enol ethers react with disodium chalcogenides to yield 2,6-disubstituted chalcogenopyranones with high selectivity. The study also examines the addition of hydrogen sulfide to diynones and the role of intermediates in the formation of chalcogenopyranones and dihydrochalcogenophenes. The research aims to improve the synthesis of chalcogenopyranones, which have applications in various fields including as electron-accepting materials in electrophotography and as heat-generating elements in optical recording.
10.1021/jo00139a031
The research explores the synthesis and properties of (E,E)-thiacyclodeca-4,7-diene (1) and its 3-methyl derivative (14) using D-mannitol as the starting material. The purpose of the study was to investigate the stereochemical and conformational behavior of these chiral compounds, which have interesting geometrical properties making them good candidates for such studies. The synthesis involved a series of stereospecific reactions, including the use of enantiomerically pure D-mannitol, (R,R)-cis-2,6-dioxabicyclo[3.3.0]octane (2), (R,R)-1,6-dibromohexane-3,4-diol (3), and various reagents like sodium sulfide, vinylmagnesium bromide, and t-BuOK. The key conclusion was that the synthesized compounds undergo rapid enantiomerization, with an energy barrier of approximately 11 kcal/mol, making them optically inactive. The study also revealed that the flipping motion of the sulfur atom has an energy barrier of around 6 kcal/mol. These findings highlight the dynamic behavior of these compounds and provide insights into their conformational motions.