Sodium Dithionite → 4-Bromo-2-(2,2-dimethoxyethyl)aniline

HRID 1668460Notes

Reaction equation

HRID 1668460 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-])=O)=[C:4]([CH2:11][CH:12]([O:15][CH3:16])[O:13][CH3:14])[CH:3]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+].C(=O)(O)[O-].[Na+]>C(O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([CH2:11][CH:12]([O:15][CH3:16])[O:13][CH3:14])[CH:3]=1

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 516892Sodium BicarbonateHCID 590046464-Bromo-2-(2,2-dimethoxyethyl)-1-nitrobenzene

Product 1

HCID 590046094-Bromo-2-(2,2-dimethoxyethyl)anilineYield 47.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Compound 66 (75 mg, 0.259 mmol) was dissolved in anhydrous ethanol (10 mL) in a dry argon purged flask fitted with a magnetic stir bar and condenser. Sodium dithionite (158.8 mg, 0.776 mmol) and sodium bicarbonate (130.6 mg, 1.554 mmol) are added to the flask and mixture heated to reflux for 24 hours. After cooling to room temperature, the reaction was quenched by the addition of H2O (10 mL) and the ethanol removed under reduced pressure. The resulting aqueous layer was transferred to a separatory funnel and extracted with ethyl acetate (three times). The combined organic layers were washed with brine, dried over sodium sulphate, filtered, concentrated and the residue purified via chromatography on silica gel (methanol:CH2Cl2, 2:98) to yield a brown oil, 67 (32 mg, 47.5%). 1H NMR (CDCl3) δ 2.83 (d, 2H, J=5.3 Hz), 3.38 (s, 6H), 4.48 (t, 1H, J=5.3 Hz), 6.61 (d, 1H, J=8.2 Hz), 7.13 (d, 1H, J=2.2 Hz), 7.15-7.17 (m, 1H); ESI-MS (m/z, %): 198/200 (M+−2MeO, 100%).

Workup

  1. customfitted with a magnetic stir bar and condenser
  2. temperatureheated
  3. temperatureto reflux for 24 hours
  4. customthe reaction was quenched by the addition of H2O (10 mL)
  5. customthe ethanol removed under reduced pressure
  6. customThe resulting aqueous layer was transferred to a separatory funnel
  7. extractionextracted with ethyl acetate (three times)
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over sodium sulphate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customthe residue purified via chromatography on silica gel (methanol:CH2Cl2, 2:98)

Sources & evidence

ORD record
ord-945e3c0d470244abbf24c862108876e9
Source dataset
uspto-grants-2011_08
Patent number
US07989447B2

Reaction notes

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