Thionyl Chloride → 2-Chloro-3-(4-chlorophenylsulfonylmethyl)pyridine

HRID 748715Notes

Reaction equation

HRID 748715 reaction equation
[Cl:1][C:2]1[C:7]([CH2:8]O)=[CH:6][CH:5]=[CH:4][N:3]=1.S(Cl)(Cl)=O.[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([S:21]([O-:23])=[O:22])=[CH:17][CH:16]=1.[Na+].C([O-])(=O)C.[K+]>C(Cl)(Cl)Cl>[Cl:1][C:2]1[C:7]([CH2:8][S:21]([C:18]2[CH:19]=[CH:20][C:15]([Cl:14])=[CH:16][CH:17]=2)(=[O:23])=[O:22])=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 24386Thionyl ChlorideHCID 517044Potassium AcetateHCID 2763647(2-Chloropyridin-3-yl)methanolHCID 23664783Sodium 4-chlorobenzenesulfinate

Product 1

HCID 230286692-Chloro-3-(4-chlorophenylsulfonylmethyl)pyridine

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A chloroform (10 ml) solution of (2-chloropyridin-3-yl)methanol (204 mg, 1.42 mmol) and thionyl chloride (0.31 ml, 4.26 mmol) was stirred at 50° C. for 8.5 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in butanol (15 ml), followed by the addition of sodium 4-chlorobenzenesulfinate (423 mg, 2.13 mmol) and potassium acetate (418 mg, 4.26 mmol). The mixture was stirred at 70 to 80° C. for 15 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. Ethyl acetate was added to the residue, and the mixture was washed successively with a saturated aqueous solution of sodium bicarbonate and brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure. The residue was subjected to flash chromatography on a silica gel column, and the fraction obtained from the hexane:ethyl acetate (=2:1) eluate was concentrated under reduced pressure, whereby the title compound (252 mg, 59%) was obtained as a white solid.

Workup

  1. concentrationthe reaction mixture was concentrated under reduced pressure
  2. dissolutionThe residue was dissolved in butanol (15 ml)
  3. temperatureAfter cooling to room temperature
  4. concentrationthe reaction mixture was concentrated under reduced pressure
  5. additionEthyl acetate was added to the residue
  6. washthe mixture was washed successively with a saturated aqueous solution of sodium bicarbonate and brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationAfter filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customthe fraction obtained from the hexane
  11. concentrationethyl acetate (=2:1) eluate was concentrated under reduced pressure, whereby the title compound (252 mg, 59%)
  12. customwas obtained as a white solid

Sources & evidence

ORD record
ord-710b6ad3445947c79396097da5ecc366
Source dataset
uspto-grants-2008_07
Patent number
US07399775B2

Reaction notes

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