Water → 5-Amino-2-neopentyloxybenzonitrile

HRID 2216385Notes

Reaction equation

HRID 2216385 reaction equation
[Cl-].[NH4+].O.[CH2:4]([O:9][C:10]1[CH:17]=[CH:16][C:15]([N+:18]([O-])=O)=[CH:14][C:11]=1[C:12]#[N:13])[C:5]([CH3:8])([CH3:7])[CH3:6]>[Fe].C(O)C>[NH2:18][C:15]1[CH:16]=[CH:17][C:10]([O:9][CH2:4][C:5]([CH3:8])([CH3:7])[CH3:6])=[C:11]([CH:14]=1)[C:12]#[N:13]

Participants

6

Reactant 3

HCID 962WaterHCID 25517Ammonium ChlorideHCID 21942316HCID 21942316, compound

Product 1

HCID 178227345-Amino-2-neopentyloxybenzonitrileYield 99.7%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Conditions

Temperature
65 °C

Procedure

To a dimethylformamide solution (364 ml) containing 2-chloro-5-nitrobenzonitrile (91 g) and neopentyl alcohol (52 g) was added sodium hydride (60% contained, 27.8 g) under ice-cooling, and the mixture was stirred for 1 hr. Water was added to the reaction mixture and the mixture was extracted with toluene. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. Diisopropyl ether was added to the residue to allow crystallization and the crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane to give 2-neopentyloxy-5-nitrobenzonitrile (105 g). Subsequently, ammonium chloride (10 g) and iron powder (75 g) were added to a mixed solvent of water (286 ml) and ethanol (753 ml) and the mixture was heated to 65° C. 2-Neopentyloxy-5-nitrobenzonitrile (80.5 g) was added by portions over 20 min and the mixture was stirred at the refluxing temperature for 30 min. The reaction mixture was ice-cooled and filtrated. The solvent was evaporated under reduced pressure. An aqueous sodium hydroxide solution was added and the mixture was extracted with toluene. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. Diisopropyl ether was added to the residue to allow crystallization and the crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane to give the title compound (70 g). melting point: 55-56° C.

Workup

  1. temperaturecooled
  2. filtrationfiltrated
  3. customThe solvent was evaporated under reduced pressure
  4. additionAn aqueous sodium hydroxide solution was added
  5. extractionthe mixture was extracted with toluene
  6. washThe organic layer was washed with saturated brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe solvent was evaporated under reduced pressure
  9. additionDiisopropyl ether was added to the residue
  10. customcrystallization
  11. customthe crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane

Sources & evidence

ORD record
ord-082a99a19413416da84ac83518998cb8
Source dataset
uspto-grants-2006_09
Patent number
US07112594B2

Reaction notes

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