Chloromethyl Methyl Ether → 4-(Methoxymethoxy)-2-nitroaniline

HRID 1356643Notes

Reaction equation

HRID 1356643 reaction equation
[H-].[Na+].[NH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12].[CH3:14][O:15][CH2:16]Cl>C1COCC1>[CH3:14][O:15][CH2:16][O:10][C:7]1[CH:8]=[CH:9][C:4]([NH2:3])=[C:5]([N+:11]([O-:13])=[O:12])[CH:6]=1

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 24758Sodium hydrideHCID 37588824-Amino-3-Nitrophenol

Product 1

HCID 185092024-(Methoxymethoxy)-2-nitroanilineYield 60%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of sodium hydride (60%, 2.70 g (67.5 mmol)) in THF (100.0 ml), under cooling with ice and with stirring, 4-amino-3-nitrophenol (10.0 g (64.9 mmol)) was added. To the resulting mixture, after 10 minutes' stirring under cooling with ice, chloromethyl methyl ether (5.50 g (68.3 mmol)) was added dropwise and the mixture was stirred at 5° C. for one hour and at room temperature for one hour, and then concentrated under reduced pressure. The residue was dissolved in ethyl acetate, washed with water and saturated aqueous solution of sodium bicarbonate successively, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. Then the residue was subjected to silica gel column chromatography with chloroform-ethanol (100:1) as eluent to give 7.69 g (60%) of 4-methoxymethoxy-2-nitroaniline as red oil.

Workup

  1. temperatureunder cooling with ice
  2. stirringTo the resulting mixture, after 10 minutes' stirring
  3. additionwas added dropwise
  4. stirringthe mixture was stirred at 5° C. for one hour and at room temperature for one hour
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in ethyl acetate
  7. washwashed with water and saturated aqueous solution of sodium bicarbonate successively
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ac45481e09794d06a2dadbb180625e03
Source dataset
uspto-grants-2003_07
Patent number
US06586617B1

Reaction notes

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