Hydrogen Peroxide → 3-Bromo-6-methoxy-2-(4-methoxyphenyl)benzothiophene 1-oxide

HRID 332852Notes

Reaction equation

HRID 332852 reaction equation
[Br:1][C:2]1[C:3]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][C:4]=2[S:5][C:6]=1[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1.FC(F)(F)C(O)=[O:24].OO.S(=O)(O)[O-].[Na+]>C(Cl)Cl.O>[Br:1][C:2]1[C:3]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][C:4]=2[S:5](=[O:24])[C:6]=1[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 8509423-Bromo-6-methoxy-2-(4-methoxyphenyl)-benzo[b]thiopheneHCID 23665763Sodium Bisulfite

Product 1

HCID 159594683-Bromo-6-methoxy-2-(4-methoxyphenyl)benzothiophene 1-oxideYield 88%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-bromo-6-methoxy-2-(4-methoxyphenyl)-benzo[b]thiophene (4 g, 11.45 mmol) in DCM (20.02 mL) at room temperature was added trifluoroacetic acid (20.02 mL) dropwise, the reaction went from orange to dark brown in color. Upon addition the resulting mixture was stirred at room temp for 10 min and then hydrogen peroxide (30% wt. aq) (1.583 mL, 16.47 mmol) was added dropwise. After 90 min at room temperature the reaction mixture was quenched with sodium bisulfite (1.714 g, 16.47 mmol) (vigorous bubbling was observed) followed by 3.0 mL of water. The resulting suspension was stirred vigorously for 15 min and then concentrated in vacuo to remove DCM and most of the TFA. The residue was partitioned between DCM (40 mL) and sat. aq. NaHCO3 solution (40 mL) and separated. The organic layer was collected (phase separator) and concentrated in vacuo to afford the crude product, which was purified by column chromatography (SiO2, 1-40% EtOAc/Heptane) to afford 3-bromo-6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene 1-oxide (4.6 g, 10.08 mmol, 88% yield) as an orange solid. 1H NMR (400 MHz, CD3OD) δ ppm=7.51-7.65 (m, 2H), 7.37-7.51 (m, 2H), 7.08 (dd, J=2.27, 8.34 Hz, 1H), 6.79-6.96 (m, 2H), 3.74 (s, 3H), 3.68 (s, 3H).

Workup

  1. additionUpon addition the resulting mixture
  2. stirringThe resulting suspension was stirred vigorously for 15 min
  3. concentrationconcentrated in vacuo
  4. customto remove DCM
  5. customThe residue was partitioned between DCM (40 mL) and sat. aq. NaHCO3 solution (40 mL)
  6. customseparated
  7. customThe organic layer was collected (phase separator)
  8. concentrationconcentrated in vacuo
  9. customto afford the crude product, which
  10. customwas purified by column chromatography (SiO2, 1-40% EtOAc/Heptane)

Sources & evidence

ORD record
ord-4e5c2d4eef054dc39995f633e5823636
Source dataset
uspto-grants-2014_11
Patent number
US08877801B2

Reaction notes

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