Scalable Synthesis of S-Fluoromethyl Benzenesulfonothioate

Abstract

A general and practical method for the preparation of S-fluoromethyl benzenesulfonothioate on a 500 g scale in two steps from readily available CH 2 FCl, sulfur, and sodium benzenesulfinate is reported. The reaction was found to be rather sensitive to water and temperature. Furthermore, the main side product of the reaction was identified to be S-phenyl benzenesulfonothioate.

A Versatile, Electrophilic Reagent for Monofluoromethylthiolation†

“…The first direct electrophilic monofluoromethylthiolating reagent, S ‐(fluoromethyl) benezenesulfonothioate (PhSO 2 SCH 2 F) which could be synthesized in kilogram‐scale was developed by our group in 2017. [ 10,12 ] This reagent was smoothly synthesized by treatment of easily available PhSO 2 Na with CH 2 FI in two steps. In the presence of a copper catalyst, PhSO 2 SCH 2 F coupled with a variety of aryl boronic acids to give the corresponding monofluoromethylthiolated arenes in high yields.…”