A Novel, Practical Synthesis of Sulfonyl Chlorides from Thiol and Disulfide Derivatives

Abstract

Hydrogen peroxide, in the presence of zirconium tetrachloride, is a very efficient reagent for the direct oxidative conversion of thiol and disulfide derivatives into the corresponding sulfonyl chlorides with high purity through oxidative chlorination. Excellent yields, very short reaction times, mild reaction conditions, and the avoidance of harsh reagents are the main advantages of this method.

Key words

oxidative chlorination - sulfonyl chloride - thiol - disulfide - hydrogen peroxide - zirconium tetrachloride

References and Notes

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13

Zirconium tetrachloride, hydrogen peroxide (30%) as well as all the thiol derivatives employed as substrates are commercial products (Merck chemical company) and were used without further purification. Disulfides were prepared according to our previously reported procedure.^¹4Melting points were determined in a capillary tube and are uncorrected. ^¹H NMR and ^¹³C NMR spectra were recorded on a Bruker-200 NMR spectrometer using TMS as internal standard. The concentration of the commercial 30% H₂O₂ solution was checked iodometrically prior to use. Synthesis of Sulfonyl Chlorides; General Procedure: A mixture of thiol (1 mmol), 30% H₂O₂ (3 mmol, 0.3 mL) and ZrCl₄ (1 mmol, 0.233 g) was stirred in MeCN (5 mL) at 25 ˚C for the appropriate time. After completion of the reaction as indicated by TLC, the reaction mixture was quenched by adding H₂O (10 mL), and extracted with EtOAc (4 × 5 mL). The extract was dried with anhydrous MgSO₄ and the filtrate was evaporated under vacuum to afford the analytically pure product (Table  [²] ). An identical procedure was employed using 30% H₂O₂ (2 mmol, 0.2 mL) and ZrCl₄ (1 mmol, 0.233 g) for the oxidative chlorination of disulfides (Table  [³] ). All of the products are known compounds and were easily characterized by comparison with authentic samples (^¹H NMR, ^¹³C NMR, mp).