Dimethyl Sulfide → HCID 21869075, compound

Participants

Reaction Conditions

Reaction Steps

In a 3-necked, round bottom flask equipped with a mechanical stirrer 2-phenoxyaniline (37.0 g, 0.2 mol) was dissolved in dichloromethane (350 mL). A vigreux column was attached and part of the dichloromethane (100 mL) was distilled off. The reaction solution was then cooled to −5° C. using a dry ice/acetone bath. Dimethyl sulfide (18 mL, 0.25 mol) was added while the temperature of the reaction solution was maintained between −5 and 0° C. Then N-chlorosuccinimide (27.0 g, 0.2 mol) was added over a 10 minute period while the temperature of the reaction mixture was maintained between −5 and 0° C. After addition was complete, an ice/water bath was substituted for the dry ice/acetone bath to maintain the temperature near 0° C. while the reaction mixture was stirred for 30 minutes. Then triethylamine (60 mL, 0.42 mol) was added, and the mixture was heated at reflux for 2 hours. After the reaction mixture cooled to room temperature, a solution of sodium sulfite (20 g) in water (500 mL) was added to the stirred reaction mixture. After 10 minutes, the reaction mixture was decanted, and the organic layer was washed with water (500 mL). A 250 mL, 3-necked round bottom flask was fitted with a distillation head and an addition funnel. Part of the organic layer (100 mL) was poured into the flask, and the remainder of the organic layer was poured into the addition funnel. The organic layer material was added to the flask in 50 mL portions while solvent was removed by distillation. After all of the organic layer had been added and the flask temperature reached 110° C., the residual material was cooled to room temperature and diluted with cyclohexane (50 mL). The mixture was then heated to 60° C., and acetic anhydride (20 mL) was added over a 15 minute period. After the reaction mixture was held at 60° C. for one hour, it was cooled to room temperature and seeded with product crystals. After the mixture was stirred for one hour, the product was collected by filtration. The collected material was repeatedly washed with hexanes and petroleum ether and dried in vacuo to provide a crystalline product (24.41 g, 59% yield, 98% purity by gas chromatography area). This product was purified by recrystallization from toluene to afford product (13.24 g) that showed no impurity peaks by gas chromatography and 1H NMR.

Provenance & Evidence