Dinitrogen Tetroxide Impregnated Activated Charcoal (N₂O₄/Charcoal): ­Selective Oxidation of Sulfides to Sulfoxides and Disulfides to Thiosulfonates

Abstract

Dinitrogen tetroxide was easily impregnated on activated charcoal to give a stable heterogeneous reagent (N₂O₄/charcoal). The chemoselective oxidation of sulfides to sulfoxides in the ­presence of different sensitive functional groups was achieved ­using this reagent in CH₂Cl₂ at room temperature. Dialkyl sulfides were also selectively converted to their corresponding sulfoxides in the presence of diaryl or alkyl-aryl sulfides. Oxidation of disulfides to thiosulfonates without any over oxidation was also performed at room temperature by this system.

Key words

dinitrogen tetroxide - activated charcoal - sulfide - ­sulfoxide - disulfide - thiosulfonate - oxidation

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4

Preparation of Dinitrogen Tetroxide Impregnated Activated Charcoal: [CAUTION: nitrogen oxides (N₂O₄ and NO₂) are toxic and corrosive gases. The use of an efficient hood and handling with special care is recommended.] To a suspension of dry activated charcoal (20.0 g) in dry CH₂Cl₂ (150 mL) at 0 °C, excess of liquid N₂O₄ (12 mL) was added while the solution was gently stirred. After 1 h, dry N₂ gas was bubbled through the solution in order to remove the excess of NO₂ gas and then the solvent was evaporated under reduced pressure. The solid reagent was filtered and dried under vacuum at 0 °C to give N₂O₄/charcoal (34.0 g). 0.22 g of this reagent contains 1 mmol N₂O₄.

9

Typical Reaction Conditions are Described for Oxidation of Benzyl Phenyl Sulfide: N₂O₄/charcoal (0.44 g) was added to a stirred solution of benzyl phenyl sulfide (0.20 g, 1 mmol) in CH₂Cl₂ (5 mL) at r.t. Monitoring of the reaction mixture by GLC showed that reaction was completed after 4 h. The reaction mixture was filtered. Evaporation of the solvent under reduced pressure followed by chromatography on a short column of silica gel using petroleum ether/Et₂O (10:1) yielded benzyl phenyl sulfoxide (0.201 g, 93%), mp 121-123 °C (lit. [17] mp 122-123 °C).

12

Typical Reaction Conditions are Described for Oxidation of Phenyl Disulfide: N₂O₄/charcoal (0.88 g) was added to a stirred solution of phenyl disulfide (0.218 g, 1 mmol) in CH₂Cl₂ (5 mL) at r.t. Monitoring of the reaction mixture by GLC showed that reaction was completed after 30 min. The reaction mixture was then filtered. Evaporation of the solvent under reduced pressure followed by chromatography on a short column of silica gel using petroleum ether/Et₂O (4:1) yielded (S)-phenyl benzenethiosulfonate (0.225 g, 90%), mp 40-41 °C (lit. [18a] mp 41-42 °C).