4-Aminophenol → 2-(4-Aminophenoxy)acetonitrile

HRID 44208Notes

Reaction equation

HRID 44208 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[NH2:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1.Br[CH2:16][C:17]#[N:18]>C(#N)C>[NH2:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][CH2:16][C:17]#[N:18])=[CH:10][CH:9]=1

Participants

5

Reactant 3

HCID 4034-AminophenolHCID 10796Cesium carbonateHCID 11534Bromoacetonitrile

Product 1

HCID 24549622-(4-Aminophenoxy)acetonitrile

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

Cs2CO3 (1629 mg, 5 mmol) was added in one portion to a solution of 4-aminophenol (541 mg, 5 mmol) in acetonitrile (20 mL). The reaction mixture was stirred at room temperature for 30 min and cooled to 0° C. prior to the addition of a solution of bromoacetonitrile (313 μL, 5 mmol) in acetonitrile (10 mL) dropwise. After stirring at room temperature for 48 h (TLC control), the reaction mixture is filtered and the filtrate evaporated to dryness in vacuo. The residue obtained after solvent removal was purified by silica gel column chromatography (hexanes/EtOAc 1:1). The desired product was isolated as yellow-brown oil. Yield: 559 mg, 76%. TLC Rf=0.2 (hexanes/EtOAc 1:1). 1H NMR (CDCl3, 600 MHz): δ 3.56 (br.s, 2H, NH2), 4.66 (s, 2H, CH2), 6.65 (d, J=8.4 Hz, 2H), 6.83 (d, J=8.4 Hz, 2H). 13C NMR (CDCl3, 150 MHz): δ 55.28, 115.60, 116.25, 117.10, 142.42, 149.65. HRMS: Calcd. [M+H]+ m/z 149.0715, Observed 149.0689.

Workup

  1. temperaturecooled to 0° C.
  2. stirringAfter stirring at room temperature for 48 h (TLC control)
  3. filtrationthe reaction mixture is filtered
  4. customthe filtrate evaporated to dryness in vacuo
  5. customThe residue obtained
  6. customafter solvent removal
  7. customwas purified by silica gel column chromatography (hexanes/EtOAc 1:1)

Sources & evidence

ORD record
ord-3b5b6f7365854c9cafb13e1bbf725566
Source dataset
uspto-grants-2013_09
Patent number
US08541415B2

Reaction notes

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