Acetaldehyde → 3-(Ethylamino)benzonitrile

HRID 591142Notes

Reaction equation

HRID 591142 reaction equation
C[O-].[Na+].[NH2:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][CH:12]=1)[C:8]#[N:9].[CH:13](=O)[CH3:14].[BH4-].[Na+].[OH-].[Na+]>CO>[CH2:13]([NH:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][CH:12]=1)[C:8]#[N:9])[CH3:14]

Participants

7

Reactant 5

HCID 177AcetaldehydeHCID 14798Sodium HydroxideHCID 167023-AminobenzonitrileHCID 4311764Sodium borohydrideHCID 10942334Sodium Methoxide

Product 1

HCID 197619053-(Ethylamino)benzonitrileYield 70.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent3×

Procedure

Sodium methoxide (4.05 g, 75 mmol) is added into methanol (45 ml) and is dissolved under stirring, and to this solution is added a solution of 3-aminobenzonitrile (17.70 g, 150 mmol) in methanol (60 ml) dropwise and the resulting mixture is stirred at room temperature for 0.5 h. Then the reaction mixture is poured into a solution of acetaldehyde (8.8 g, 200 mmol) in methanol (100 ml) and is stirred at room temperature for 5.0 h. The mixture is added with NaBH4 (6.00 g, 150 mmol) in portions and is stirred at room temperature for 10 min, and then is refluxed at elevated temperature for 10 min. The reaction mixture is cooled under ice-water bath, added with 10% NaOH (aq) (90 ml) dropwise and is stirred for 5 min. Methanol is removed under reduced pressure, and the left aqueous solution is extracted with ethyl acetate (150 ml*2). The organic phases are combined, washed with saturated brine (100 ml) and separated, dried over anhydrous sodium sulfate, and concentrated to give a oily crude product (22.1 g). The crude product is purified by neutral alumina column chromatography (eluent: petroleum ether/CH2Cl2=2/1) to give a light yellow oily target product (15.4 g, yield: 70.2%).

Workup

  1. dissolutionis dissolved
  2. stirringthe resulting mixture is stirred at room temperature for 0.5 h
  3. stirringis stirred at room temperature for 5.0 h
  4. stirringis stirred at room temperature for 10 min
  5. temperatureis refluxed at elevated temperature for 10 min
  6. temperatureThe reaction mixture is cooled under ice-water bath
  7. stirringis stirred for 5 min
  8. customMethanol is removed under reduced pressure
  9. extractionthe left aqueous solution is extracted with ethyl acetate (150 ml*2)
  10. washwashed with saturated brine (100 ml)
  11. customseparated
  12. dry with materialdried over anhydrous sodium sulfate
  13. concentrationconcentrated
  14. customto give a oily crude product (22.1 g)
  15. customThe crude product is purified by neutral alumina column chromatography (eluent: petroleum ether/CH2Cl2=2/1)

Sources & evidence

ORD record
ord-5e79bb71be0b486199b84cfc83e2b35c
Source dataset
uspto-grants-2016_01
Patent number
US09238632B2

Reaction notes

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