Generation and Rearrangements of Thioacetaldehyde S-Sulfide (Methylthiosulfine) and Thioacetone S-Sulfide (Dimethylthiosulfine)

✍ Scribed by Günther Maier; Hans Peter Reisenauer; Jaroslaw Romański; Holm Petzold; Grzegorz Mlostoń

• Book ID: 102177546
• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 175 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200600151

✦ Synopsis

Abstract

Matrix isolation spectroscopy allows the direct identification of ylides 1b and 1c. They are generated by flash vacuum pyrolysis of the 1,2,4‐trithiolanes 3b and 3c. Photochemical activation of the thiosulfines 1b and 1c initiates ring closure to the corresponding dithiiranes 2b and 3b. The presence of a methyl group in thiosulfines 1b and 1c opens a new reaction channel for their thermal transformation, namely a [1,4]‐H shift with formation of vinyldisulfanes 5. The results of the matrix studies are supported by preparative runs, in which the products of the pyrolyses were trapped at higher temperatures and their spectra measured in solution under standard conditions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)