反应详情

温度

1 °C

A 50-L, 5-necked flask equipped with a mechanical stirrer, a thermometer, and a 1-L addition funnel was charged with 3-acetyl-5-chloro-2-thiophenesulfonamide (3, 1.087 kg, 4.55 mol) and ethyl acetate (22L). The pale yellow suspension was cooled to 1° C. over 45 minutes using an ice-water bath, and 90% pyridinium bromide perbromide (1.305 kg, 3.67 mol) was added in one portion. Sulfuric acid (544 mL) was added via the addition funnel over 10 minutes causing the temperature to rise to 5° C. The reaction mixture was stirred for 1 hour, after which TLC analysis indicated complete reaction. Thirty minutes later, water (5L) was added and the mixture was stirred for 5 minutes before the phases were split. The organic phase was washed with saturated aqueous sodium chloride until the pH of the wash was 3 (4×5L required), dried over sodium sulfate (1 kg), filtered, and stripped of solvent by rotary evaporation. The residue was triturated with methylene chloride (2L) and chilled for 15 minutes before the solid was collected by filtration, washed with cold methylene chloride (2L), and dried in air at ambient temperature to a constant weight of 1.041 kilograms (72%) of 4: mp 147°-148° C.; IR (KBr) 3381, 3263, 3093, 1694, 1532, 1403, 1336, 1163, 1102 cm-1 ; 1H NMR (acetone-d6) δ 7.76 (s, 1H), 7.11 (br, 2H), 4.76 (s, 2H); Analysis for C6H5BrClNO3S2 : Calcd: C, 22.62; H, 1.58; N, 4.40; S, 20.13. Found: C, 22.66; H, 1.60; N, 4.35; S, 20.12.

1. customto rise to 5° C
2. customreaction
3. stirringthe mixture was stirred for 5 minutes before the phases
4. customwere split
5. washThe organic phase was washed with saturated aqueous sodium chloride until the pH of the wash
6. dry with materialdried over sodium sulfate (1 kg)
7. filtrationfiltered
8. customstripped of solvent by rotary evaporation
9. customThe residue was triturated with methylene chloride (2L)
10. temperaturechilled for 15 minutes before the solid
11. filtrationwas collected by filtration
12. washwashed with cold methylene chloride (2L)
13. dry with materialdried in air at ambient temperature to a constant weight of 1.041 kilograms (72%) of 4