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Flash Vacuum Thermolysis of 4H-3,1-Benzoxathiin-4-thione: UV-Photoelectron Spectroscopy Characterization and Quantum Chemistry Studies

✍ Scribed by Tomasz Drewnowski; Anna Chrostowska; Stanisław Leśniak; Alain Dargelos; Saïd Khayar

Publisher: John Wiley and Sons
Year: 2008
Tongue: German
Weight: 592 KB
Volume: 91
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.200890079

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✦ Synopsis

Abstract

The mechanism of the reaction of 4__H__‐3,1‐benzoxathiin‐4‐thione (3) under flash vacuum thermolysis conditions has been studied by UV‐photoelectron spectra. It was shown that in the first step of the reaction at 400° 3 underwent the Schönberg–Newman–Kwart rearrangement to give 4__H__‐1,3‐benzodithiin‐4‐one (6). Increasing of the temperature to 650° resulted in the elimination of thioformaldehyde and the formation of benzothiet‐2‐one (1). Subsequent elevation of the temperature prompted presumably the ring opening of 1 to (6‐thioxocyclohexa‐2,4‐dien‐1‐ylidene)methanone (7) (at 680°), which at 700° eliminated CO and underwent a Wolff‐type ring contraction to give (cyclopenta‐2,4‐dien‐1‐ylidene)methanethione (2). UV‐Photoelectron spectra were recorded at different steps of the reaction and analyzed considering the theoretical evaluation of ionization potentials.

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