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Generation and Rearrangements of Thioacetaldehyde S ‐Sulfide (Methylthiosulfine) and Thioacetone S ‐Sulfide (Dimethylthiosulfine)
Author(s) -
Maier Günther,
Reisenauer Hans Peter,
Romański Jaroslaw,
Petzold Holm,
Mlostoń Grzegorz
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200600151
Subject(s) - chemistry , matrix isolation , sulfide , flash vacuum pyrolysis , pyrolysis , spectroscopy , matrix (chemical analysis) , photochemistry , infrared spectroscopy , medicinal chemistry , organic chemistry , physics , chromatography , quantum mechanics
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)