Ethyl Acetate → 5-Bromo-2-morpholin-4-ylaniline

HRID 1431269Notes

Reaction equation

HRID 1431269 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[C:4]([N+:14]([O-])=O)[CH:3]=1.CCOC(C)=O.[Sn](Cl)Cl>>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:9][CH2:10][O:11][CH2:12][CH2:13]2)=[C:4]([CH:3]=1)[NH2:14]

Participants

4

Reactant 3

HCID 8857Ethyl AcetateHCID 24479Stannous ChlorideHCID 83701685-Bromo-2-morpholinonitrobenzene

Product 1

HCID 49618715-Bromo-2-morpholin-4-ylaniline

Procedure

To a solution of 4-(4-bromo-2-nitrophenyl)morpholine (13.2 g, 46 mmol) dissolved in EtOAc (200.00 mL, 2043 mmol) at rt was added all in one portion tin(II) chloride dehydrate (52 g, 230 mmol). An exotherm developed and the orange color faded to a faint yellow. The reaction was stirred at ambient temperature for 15 min then heated to reflux for 45 min. After 60 min TLC indicated no starting material remained and the reaction was equilibrated to rt. The reaction was washed with 200 mL 5N aq. Sodium hydroxide solution followed by 100 mL water and 50 mL brine. The organic separation was stirred over anhydrous magnesium sulfate, filtered and the filtrate concd under reduced pressure to afford a pale yellow solid. Mass Spectrum (ESI) m/e=257.0 & 259.0 (M+1).

Workup

  1. temperaturethen heated
  2. temperatureto reflux for 45 min
  3. waitAfter 60 min TLC indicated
  4. customwas equilibrated to rt
  5. washThe reaction was washed with 200 mL 5N aq. Sodium hydroxide solution
  6. customThe organic separation
  7. stirringwas stirred over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customthe filtrate concd under reduced pressure to afford a pale yellow solid

Sources & evidence

ORD record
ord-c067c5556e034c69803132b46571e9f3
Source dataset
uspto-grants-2015_01
Patent number
US08940724B2

Reaction notes

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