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Updated: Feb 19, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
The Trifluoromethyl Sulfinyl and Oxathiyl Radicals
Zhuang Wu1, Jian Xu1, Guohai Deng1
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.
Abstract:
Two hitherto unreported sulfur-centered radicals CF3 SO. and CF3 OS. were generated in the gas phase through high-vacuum flash pyrolyses of sulfoxide CF3 S(O)X (X=CF3 , Cl, PhO) precursors. The CF3 OS. molecule is the first experimental example that constitutes an oxathiyl radical. It was isolated and characterized by combining matrix-isolation IR and UV/Vis spectroscopy with quantum chemical computations up to the UCCSD(T)-F12/cc-pVTZ-F12 level of theory. Upon UV light irradiation (254 or 266 nm), sulfinyl radical (CF3 SO. ) isomerizes to oxathiyl radical (CF3 OS. ) in cryogenic noble gas matrices (Ar and Ne). Natural population analyses at the BP86/def2-TZVPP//UCCSD(T)-F12/cc-pVTZ-F12 level suggest that the spin density in CF3 OS. is mainly localized on the sulfur atom (0.86), whereas, in CF3 SO. the spin density is almost equally distributed on the sulfur (0.55) and oxygen (0.43) atoms.
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