Sulfide oxidation with N-halosuccinimides

Abstract

Numerous methods have been developed for the oxidation of sulfides1p2 to sulfoxides in reactions usually giving the sulfoxide contaminated with sulfide and/or sulfone. More recently the use of t-butyl hypochlorite as a reagent for the oxidation of sulfides to sulfoxides has been r e p~r t e d .~,~ These reports prompted us to disclose our results on the use of N-halosuccinimides in methanol as the oxidizing agents. It has been previously shown5 that aromatic sulfides are oxidized cleanly to sulfoxides in aqueous media when treated with I\;-bromosuccinimide, but that aliphatic sulfides undergo C-S bond cleavage under identical conditions. I n our study, the oxidation of sulfides was carried out in anhydrous methanol employing N-bromo- (SBS) and N-chlorosuccinimide (KCS). Sulfoxides were iso-(7) P. S. NOTES 3977were characterized by their ir spectra, refractive indices, and elemental analyses.The solid sulfoxides were isolated by dissolving the mixture in 200 ml of methylene chloride and washing thoroughly with water. After the solution was dried and the solvent was evaporated, the solids were recrystallized.

A new and efficient protocol for the synthesis of the key intermediate of Palbociclib

“…It has been previously shown that aromatic sulfides are oxidized cleanly to sulfoxides in aqueous media when treated with NBS. 26,27 Tagaki et al 27 have demonstrated that certain aromatic sulfides could be oxidized to sulfoxides in 70% dioxane-containing water containing NBS in 1964. In addition, Surendra et al's 28 research also demonstrated the oxidation of sulfides to sulfoxides by β-cyclodextrin in water under neutral conditions in 2005.…”

A Mild and Efficient Synthesis of 3-Aminosubstituted Isothiazole S-Oxides and their 5-Sulfanylsubstituted Derivatives

“…A large number of procedures designed for carrying out the oxidation of sulfides to sulfoxides have been published, nevertheless most of them tried in this study resulted in low chemoselectivity and were unable to stop at the sulfoxide oxidation state [7 a-d ]. Most of the reagents tested (m-CPBA, HNO 3 /CH 3 COOH, H 2 O 2 , t-BuOOH/H 2 O/Ti(iPrO) 4 / DET, molybdenum (VI) oxodiperoxo complexes coated on silica gel, N-chloro-succinimide, oxone, MMPP) bore out this limitation [8][9][10] except sodium metaperiodate which reacted with 3-benzylaminoisothiazole (1a) affording 3-benzylaminoisothiazole 1-oxide (2a) in acceptable yields (56%) together with a small amount of 3-benzylaminoisothiazole 1,1-dioxide (3a)(14%) (Scheme 1) [11].…”

Reactions of sulfides with S‐330, a potential decontaminant of sulfur mustard in formulations

“…d Analysis by GC-MS confirmed the chlorination of the sulfoxide, but the structure of the particular isomer was not proven. observations of the reactions of sulfides with haloamides [11][12][13] and an N-sulfonyloxaziridine.…”

“…However, reactions E and F with MPS led to almost complete consumption of active chlorine, an observation supported by LC analysis of the dechlorinated glycouril after the reaction. The mechanism of the oxidation of sulfur by haloimides has been described previously 12 as a nucleophilictype attack by the sulfide on the highly positive active chlorine followed by hydrolysis of the chlorosulfonium ion. Our results were consistent with that mechanism, because the weakest nucleophile of the three sulfides, HD, gave the lowest yields of sulfoxide under similar conditions (reactions B, D and F).…”

“…d Analysis by GC-MS confirmed the chlorination of the sulfoxide, but the structure of the particular isomer was not proven. observations of the reactions of sulfides with haloamides [11][12][13] and an N-sulfonyloxaziridine. 14 Products Reactions I-IV were observed in different quantities, depending on the particular sulfide used and the amount of water in the solvent.…”