Abstract
AbstractFlash 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.
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