Bromoacetic Acid → 4-Bromo-2-ethyl-1-(methylsulfonyl)benzene

HRID 1644685Notes

Reaction equation

HRID 1644685 reaction equation
S([O-])([O-])=O.[Na+].[Na+].C(=O)(O)[O-].[Na+].[Br:12][C:13]1[CH:18]=[CH:17][C:16]([S:19](Cl)(=[O:21])=[O:20])=[C:15]([CH2:23][CH3:24])[CH:14]=1.Br[CH2:26]C(O)=O.[OH-].[Na+]>O.O1CCOCC1>[Br:12][C:13]1[CH:18]=[CH:17][C:16]([S:19]([CH3:26])(=[O:21])=[O:20])=[C:15]([CH2:23][CH3:24])[CH:14]=1

Participants

8

Reactant 5

HCID 6227Bromoacetic AcidHCID 14798Sodium HydroxideHCID 24437Sodium SulfiteHCID 516892Sodium BicarbonateHCID 27375364-Bromo-2-ethylbenzenesulfonyl chloride

Product 1

HCID 593508074-Bromo-2-ethyl-1-(methylsulfonyl)benzeneYield 100%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of sodium sulfite (4.44 g, 35.3 mmol) and sodium bicarbonate (2.96 g, 35.3 mmol) in water (100 mL) at 70° C. was added 4-bromo-2-ethyl-benzenesulfonyl chloride (5 g, 17.6 mmol) in dioxane (20 mL) drop-wise via an addition funnel. After an hour, the mixture was heated at 100° C. and bromoacetic acid (4.90 mL, 35.3 mmol) was added. After an hour, the reaction mixture was cooled to 90° C., and sodium hydroxide (2.82 g, 70.5 mmol) was added. The resulting mixture was stirred at 90° C. overnight. After cooling to room temperature, water was added to the resulting suspension. The aqueous layer was extracted with dichloromethane (250 mL×3). The collected organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated to give 4-bromo-2-ethyl-1-methanesulfonyl-benzene (4.62 g, 100%), which was used in the next step without further purification. 1H NMR (300 MHz, CDCl3) δ ppm 7.89 (d, J=8.5 Hz, 1 H), 7.56 (d, J=1.5 Hz, 1 H), 7.51 (dd, J=8.5, 1.5 Hz, 1 H), 3.07 (s, 3 H), 3.05 (q, J=7.4 Hz, 2 H), 1.33 (t, J=7.4 Hz, 3 H).

Workup

  1. waitAfter an hour
  2. waitAfter an hour
  3. temperaturethe reaction mixture was cooled to 90° C.
  4. temperatureAfter cooling to room temperature
  5. extractionThe aqueous layer was extracted with dichloromethane (250 mL×3)
  6. washThe collected organic layers were washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-ab6919b0ad09484e881f06e8a153479a
Source dataset
uspto-grants-2012_02
Patent number
US08124629B2

Reaction notes

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