Journal article

Publication year: 2012

Pages: 3408-3415

Journal: European Journal of Organic Chemistry

Volume number: 2012

Issue number: 18

ISSN: 1434-193X

DOI Link: https://doi.org/10.1002/ejoc.201200146

Publisher: Wiley

Abstract: 

Flash vacuum pyrolysis of 3,3,5,5‐tetramethyl‐1,2,4‐trithiolane 1‐oxide
performed at 700 °C yields the 1‐oxatrisulfan‐3‐yl radical (HOSS^·) along with disulfur monoxide (S₂O)
and diisopropyl sulfide, which were isolated in argon matrices at 10 K.
Upon irradiation with UV light, the 1‐oxatrisulfan‐3‐yl radical
undergoes isomerization to the 1‐oxatrisulfan‐1‐yl radical (HSSO^·).
Both radicals were identified by comparison of their computed and
experimental IR and UV/Vis spectra. In addition, density functional
theory (DFT) computations offer a plausible explanation of the most
likely reaction mechanism, suggesting that the initial step is a 1,3‐H
shift with simultaneous ring opening. A 1‐oxatrisulfane derivative
formed thereby undergoes fragmentations via a radical and a competitive
concerted pathway leading to the observed final products. The same
mechanism also governs the thermal fragmentation of di‐tert‐butyl disulfide S‐oxide. Its pyrolysis at 700 °C affords an analogous set of products, including the 1‐oxatrisulfan‐3‐yl radical (HOSS^·) as the key intermediate.

Harvard Citation style: Reisenauer, H., Mloston, G., Romanski, J. and Schreiner, P. (2012) Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS· Radical, European Journal of Organic Chemistry, 2012(18), pp. 3408-3415. https://doi.org/10.1002/ejoc.201200146

APA Citation style: Reisenauer, H., Mloston, G., Romanski, J., & Schreiner, P. (2012). Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS· Radical. European Journal of Organic Chemistry. 2012(18), 3408-3415. https://doi.org/10.1002/ejoc.201200146