Ammonium Chloride → HCID 43345909, compound

HRID 1641072Notes

Reaction equation

HRID 1641072 reaction equation
[Cl-].[NH4+].[Br:3][C:4]1[CH:9]=[CH:8][C:7]([N:10]([CH3:14])[CH2:11][CH2:12][OH:13])=[C:6]([N+:15]([O-])=O)[CH:5]=1>O.CCOC(C)=O.[Fe]>[NH2:15][C:6]1[CH:5]=[C:4]([Br:3])[CH:9]=[CH:8][C:7]=1[N:10]([CH3:14])[CH2:11][CH2:12][OH:13]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 59418670HCID 59418670, compound

Product 1

HCID 43345909HCID 43345909, compoundYield 76.3%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Iron (1.5 g, 26.2 mmol) and ammonium chloride (0.39 g, 1.0 eq) in water (8 mL) was heated to reflux for 0.5 hours. 2-((4-bromo-2-nitrophenyl)(methyl)amino)ethanol (25B) (2.0 g, 7.27 mmol) was slowly added. The reaction mixture was heated to reflux for 14 hours, cooled to rt, diluted with water and EtOAc and filtered through Celite. The aqueous phase was extracted with EtOAc. The combined organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel eluting with a gradient of PE:EtOAc 60:40-40:60, to provide 1.36 g (76%) of the desired product 2-((2-amino-4-bromophenyl)(methyl)amino)ethanol (25C): 1H NMR (300 MHz, CDCl3) δ 6.92-6.82 (3H, m), 3.68 (2H, t), 3.04 (2H, t), 2.70 (3H, s).

Workup

  1. temperatureto reflux for 0.5 hours
  2. temperatureThe reaction mixture was heated
  3. temperatureto reflux for 14 hours
  4. filtrationfiltered through Celite
  5. extractionThe aqueous phase was extracted with EtOAc
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe crude material was purified by column chromatography on silica gel eluting with a gradient of PE

Sources & evidence

ORD record
ord-17db14b9aaaa445899fccc9e8d8f9591
Source dataset
uspto-grants-2012_02
Patent number
US08114893B2

Reaction notes

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