Benzyl Alcohol → 5-benzyloxy-N-methyl-2-nitroaniline

HRID 1430403Notes

Reaction equation

HRID 1430403 reaction equation
[CH3:1][NH2:2].F[C:4]1[CH:9]=[C:8](F)[CH:7]=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12].[CH2:14]([OH:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C(=O)([O-])[O-].[K+].[K+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.C1(C)C=CC=CC=1>[CH2:14]([O:21][C:8]1[CH:7]=[CH:6][C:5]([N+:11]([O-:13])=[O:12])=[C:4]([CH:9]=1)[NH:2][CH3:1])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

8

Reactant 4

HCID 244Benzyl AlcoholHCID 6329MethylamineHCID 11430Potassium CarbonateHCID 679672,4-Difluoronitrobenzene

Product 1

HCID 679540515-benzyloxy-N-methyl-2-nitroanilineYield 96%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent2×

Conditions

Temperature
37.5 °C

Procedure

An aqueous solution of 40% methyl amine (8.2 mL, 94.2 mmol) was added dropwise to a toluene solution (50 mL) of 2,4-difluoronitrobenzene (5.0 g, 31.4 mmol) under ice cooling, and the mixture was stirred at 35-40° C. for 2 hours. Water was added to the reaction solution, and toluene extraction was performed, followed by washing with water. Benzyl alcohol (6.5 mL, 62.8 mmol), tetrabutyl ammonium bromide (1.0 g, 3.1 mmol) and potassium carbonate (5.2 g, 37.6 mmol) were added to the resulting organic layer, and the mixture was heated under reflux for 4 hours. After the reaction solution was cooled, water (25 mL) was added, and the mixture was stirred at 70° C. for 1 hour. The mixture was stirred under ice cooling for 30 minutes, and precipitated crystals were collected by filtration. The resulting crystals were washed with water and dried at 50° C., thereby obtaining 7.8 g of orange, powdery 5-benzyloxy-N-methyl-2-nitroaniline (yield: 96%).

Workup

  1. washby washing with water
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 4 hours
  4. temperatureAfter the reaction solution was cooled
  5. stirringthe mixture was stirred at 70° C. for 1 hour
  6. stirringThe mixture was stirred under ice cooling for 30 minutes
  7. customprecipitated crystals
  8. filtrationwere collected by filtration
  9. washThe resulting crystals were washed with water
  10. customdried at 50° C.

Sources & evidence

ORD record
ord-806c977f8adb4f3a86a7056da02ed655
Source dataset
uspto-grants-2015_01
Patent number
US08940889B2

Reaction notes

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