Sodium Hydroxide → Tert-butyl 3-(methylsulfonyl)benzoate

HRID 888415Notes

Reaction equation

HRID 888415 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:12]=[CH:13][CH:14]=1)[C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].[CH3:15][S:16]([O-:18])=[O:17].[Na+].N1CCC[C@H]1C(O)=O.[OH-].[Na+]>[Cu]I>[CH3:15][S:16]([C:2]1[CH:3]=[C:4]([CH:12]=[CH:13][CH:14]=1)[C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])(=[O:18])=[O:17]

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 145742L-Proline2×HCID 334079tert-Butyl 3-bromobenzoateHCID 2733271Sodium methanesulfinate2×

Product 1

HCID 59539564Tert-butyl 3-(methylsulfonyl)benzoateYield 72.4%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×

Conditions

Temperature
80 °C

Procedure

The mixture of tert-butyl 3-bromobenzoate (7.0 g, 27.2 mmol), sodium methanesulfinate (4.45 g, 43.6 mmol), copper(I) iodide (0.52 g, 2.72 mmol), L-proline (0.63 g, 5.44 mmol) and sodium hydroxide (0.22 g, 5.44 mmol) was purged with nitrogen and DMSO was added. The mixture was heated to 80° C. After 18 h, the mixture was cooled to ambient temperature. Additional sodium methanesulfinate (2.78 g, 27.2 mmol), copper(I) iodide (0.52 g, 2.72 mmol), L-proline (0.63 g, 5.44 mmol) were added and the mixture was stirred at 80° C. for another 18 h. The mixture was cooled to ambient temperature and filtered with Celite. Lithium chloride (3.0 M in water) was added and the mixture was extracted with ethyl acetate (3×). The combined organic extracts were washed with LiCl (3.0 M in water), brine, dried over sodium sulfate, filtered and concentrated. Purification by silica gel chromatography (100% hexanes→75% hexanes/ethyl acetate) gave the title compound (5.05 g).

Workup

  1. customwas purged with nitrogen and DMSO
  2. additionwas added
  3. temperaturethe mixture was cooled to ambient temperature
  4. temperatureThe mixture was cooled to ambient temperature
  5. filtrationfiltered with Celite
  6. additionLithium chloride (3.0 M in water) was added
  7. extractionthe mixture was extracted with ethyl acetate (3×)
  8. washThe combined organic extracts were washed with LiCl (3.0 M in water), brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by silica gel chromatography (100% hexanes→75% hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-d4926730436f44d09d747c62843de7e8
Source dataset
uspto-grants-2012_08
Patent number
US08247401B2

Reaction notes

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