Diethyl disulfide → 2-Bromo-5-(ethylsulfonyl)pyridine

To a solution of 2,5-dibromopyridine (2 g, 8.4 mmol) in diethyl ether (50 mL) was added n-butyl lithium (1.6 M in hexanes, 9.24 mmol) dropwise at −78° C. under a nitrogen atmosphere. After the mixture was stirred at this temperature for 1 hour, diethyldisulfide (1.15 mL, 9.24 mmol) was added slowly at −78° C., and the mixture was stirred at this temperature for 1 hour and at 0° C. for an additional 1 hour. The reaction mixture was then quenched with 1 N hydrochloric acid (20 mL). The aqueous layer was separated and extracted with diethyl ether (20 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The residue was dissolved in dichloromethane (50 mL). To the solution, m-chloroperoxybenzoic acid (4.3 g, 80% purity, 16.8 mmol) was added portion-wise at 0° C. After being stirred at room temperature for 2 hours, the mixture was treated with a saturated aqueous solution of sodium sulfite (20 mL), and stirred for 15 minutes. The organic layer was separated and washed with a saturated aqueous solution of sodium bicarbonate (20 mL), then dried over sodium sulfate, and concentrated in vacuo. The residue was purified by flash column chromatography (elution with 30% ethyl acetate in petroleum ether) to give 2-bromo-5-ethanesulfonyl-pyridine (400 mg, 19%) as a white solid (reference: Li J. et al., Bioorg. Med. Chem. 13 (2005) 1805-1809).

1. stirringthe mixture was stirred at this temperature for 1 hour and at 0° C. for an additional 1 hour
2. customThe reaction mixture was then quenched with 1 N hydrochloric acid (20 mL)
3. customThe aqueous layer was separated
4. extractionextracted with diethyl ether (20 mL)
5. dry with materialThe combined organic layers were dried over sodium sulfate
6. concentrationconcentrated in vacuo
7. dissolutionThe residue was dissolved in dichloromethane (50 mL)
8. stirringAfter being stirred at room temperature for 2 hours
9. stirringstirred for 15 minutes
10. customThe organic layer was separated
11. washwashed with a saturated aqueous solution of sodium bicarbonate (20 mL)
12. dry with materialdried over sodium sulfate
13. concentrationconcentrated in vacuo
14. customThe residue was purified by flash column chromatography (elution with 30% ethyl acetate in petroleum ether)

ORD record

ord-5a79a627bbaa445dbee2a4df11ae4ac4

Source dataset

uspto-grants-2014_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08642629B2