Sulfuric Acid → Tert-butyl 4-(bromomethyl)benzoate

HRID 1919896Notes

Reaction equation

HRID 1919896 reaction equation
S([O-])([O-])(=O)=O.[Mg+2].S(=O)(=O)(O)O.[Br:12][CH2:13][C:14]1[CH:22]=[CH:21][C:17]([C:18]([OH:20])=[O:19])=[CH:16][CH:15]=1.C(=O)(O)[O-].[Na+]>ClCCl.C(O)(C)(C)C>[Br:12][CH2:13][C:14]1[CH:22]=[CH:21][C:17]([C:18]([O:20][C:14]([CH3:22])([CH3:15])[CH3:13])=[O:19])=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 225994-(Bromomethyl)benzoic acidHCID 24083Sulfuric acid magnesium salt (1:1)HCID 516892Sodium Bicarbonate

Product 1

HCID 11414578Tert-butyl 4-(bromomethyl)benzoate

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 6386tert-ButanolSolvent

Procedure

Magnesium sulfate (7.8494 g, 65.21 mmol) was suspended in dichloromethane (65 mL). Concentrated sulfuric acid (0.9 mL) was added and allowed to stir for 15 minutes. 4-(bromomethyl)benzoic acid (3.4851 g, 16.21 mmol) and tert-butanol (7.8 mL) were added. The reaction was allowed to stir overnight at room temperature. Saturated sodium bicarbonate (15 ml) was added and the reaction was allowed to stir. Magnesium sulfate was filtered off. The reaction was washed with saturated sodium bicarbonate. The aqueous layer was extracted three times with dichloromethane. The combined organic layer was dried over sodium sulfate, filtered, and concentrated. The resulting material was dissolved in ethyl acetate and the product was partially recrystallized. To optimize the yield, the product remaining in the ethyl acetate was purified by column chromatography. 1H NMR 600 MHz (CD3OD) δ 7.91 (d, 2H, J=8.2 Hz), 7.48 (d, 2H, J=8.2 Hz), 4.58 (s, 2H), 1.60 (s, 9H).

Workup

  1. stirringto stir overnight at room temperature
  2. stirringto stir
  3. filtrationMagnesium sulfate was filtered off
  4. washThe reaction was washed with saturated sodium bicarbonate
  5. extractionThe aqueous layer was extracted three times with dichloromethane
  6. dry with materialThe combined organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. dissolutionThe resulting material was dissolved in ethyl acetate
  10. customthe product was partially recrystallized
  11. customwas purified by column chromatography

Sources & evidence

ORD record
ord-fb7612472e2349beb55cdee63c708344
Source dataset
uspto-grants-2012_05
Patent number
US08168658B2

Reaction notes

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