4-Bromophenol → 2-Bromo-3-(4-bromophenoxy)-6-methoxybenzo[b]thiophene 1,1-dioxide

HRID 632681Notes

Reaction equation

HRID 632681 reaction equation
[Br:1][C:2]1[S:6](=[O:8])(=[O:7])[C:5]2[CH:9]=[C:10]([O:13][CH3:14])[CH:11]=[CH:12][C:4]=2[C:3]=1Br.[Br:16][C:17]1[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][CH:18]=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.O>[Br:1][C:2]1[S:6](=[O:8])(=[O:7])[C:5]2[CH:9]=[C:10]([O:13][CH3:14])[CH:11]=[CH:12][C:4]=2[C:3]=1[O:23][C:20]1[CH:21]=[CH:22][C:17]([Br:16])=[CH:18][CH:19]=1

Participants

6

Reactant 3

HCID 78084-BromophenolHCID 10796Cesium carbonateHCID 161275842,3-Dibromo-6-methoxybenzo[b]thiophene 1,1-dioxide

Product 1

HCID 867306362-Bromo-3-(4-bromophenoxy)-6-methoxybenzo[b]thiophene 1,1-dioxideYield 93.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 2,3-dibromo-6-methoxybenzo[b]thiophene 1,1-dioxide (12.5 g, 35.3 mmol) in THF (175 mL) at room temperature was added 4-bromophenol (6.49 g, 37.1 mmol) and Cs2CO3 (34.5 g, 106 mmol). The resulting suspension was warmed to 50° C. and the reaction turned faintly yellowish green after a few minutes and then subsequently faintly pink, the mixture remained a suspension. After 4 h at 50° C. the mixture was cooled to room temperature, diluted with water (175 mL), and stirred for 15 min. The solution was transferred to a separator funnel and the phases were separated. The aqueous layer was extracted with EtOAc (3×100 mL) and the combined organic layers were then washed with brine (100 mL), dried over anhydrous Na2SO4, filtered and concentrated in vacuo to afford 2-bromo-3-(4-bromophenoxy)-6-methoxybenzo[b]thiophene 1,1-dioxide (14.7 g, 33.0 mmol, 93% yield) as a faintly pink solid which was used without further purification. 1H NMR (400 MHz, CDCl3) δ ppm==3.83 (s, 3H), 6.92-7.03 (m, 3H), 7.25-7.35 (m, 2H), 7.39-7.50 (m, 2H).

Workup

  1. waitthe reaction turned faintly yellowish green after a few minutes
  2. temperatureAfter 4 h at 50° C. the mixture was cooled to room temperature
  3. customThe solution was transferred to a separator funnel
  4. customthe phases were separated
  5. extractionThe aqueous layer was extracted with EtOAc (3×100 mL)
  6. washthe combined organic layers were then washed with brine (100 mL)
  7. dry with materialdried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5893f2f3c0044df2b4d7d1ebf5cc3dcb
Source dataset
uspto-grants-2016_04
Patent number
US09321746B2

Reaction notes

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