Reactions of acetylenes, possessing bulky alkyl substituents, with S2Cl2. Unexpected formation of α-oxothioketones, thiirene 1-oxides, and 1,2-dithietes

✍ Scribed by Juzo Nakayama; Kenta Takahashi; Toshiaki Watanabe; Yoshiaki Sugihara; Akihiko Ishii

• Publisher: Elsevier Science
• Year: 2000
• Tongue: French
• Weight: 90 KB
• Volume: 41
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)01475-1

✦ Synopsis

The reaction of di-t-butylacetylene with S 2 Cl 2 , followed by purification with silica-gel column chromatography, gave 2,2,5,5-tetramethyl-4-oxo-3-hexanethione (4a) (37%) and 2,3-di-t-butylthiirene 1-oxide (5a) (10%), which were formed by hydrolysis of the initial product, 2,3-di-t-butyl-2,3-dichloroepisulfide (3a). The same work-up of the reaction mixture of di(1-adamantyl)acetylene with S 2 Cl 2 provided 2oxoethanethione (4b) (4-33%), thiirene 1-oxide (5b) (8-27%) and 1,2-dithiete (9b) (3-21%). The reaction of 2,2,5,5,6,6,9,9-octamethyl-3,7-decadiyne (1c) with S 2 Cl 2 furnished a 4H,5H-thiepin (12) as the sole product in 99% yield.