Acetic Acid → 4-(1-aminoethyl)benzonitrile

HRID 448651Notes

Reaction equation

HRID 448651 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C:9](=O)[CH3:10])=[CH:5][CH:4]=1)#[N:2].C([O-])=O.[NH4+:15].C(O)(=O)C>[Ir].CO>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH:9]([NH2:15])[CH3:10])=[CH:5][CH:4]=1)#[N:2]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 740444'-CyanoacetophenoneHCID 2723923Ammonium formate

Product 1

HCID 115447904-(1-aminoethyl)benzonitrile

Reagents, catalysts & solvents 2

HCID 23924IridiumCatalystHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

726 mg (5.0 mmol) of 4′-cyanoacetophenone (MW: 145.16), 946 mg (15.0 mmol) of ammonium formate (MW: 63.06) and 5.90 mg (0.01 mmol, S/C=500) of the iridium catalyst Ir-7 (MW: 590.13) were introduced in a 20-mL Schlenk tube, and subjected to argon-gas replacement. To this, 5 mL of dehydrated methanol and 286 μL (5.0 mmol) of acetic acid were added and stirred while heating at 60° C. for 3 hr. After distillation of the solvent, a saturated sodium hydrogen carbonate solution was added, then a product was extracted with methylene chloride, the organic layer was washed with water, and the product was dried with sodium sulfate. The drying agent was removed by filtration and the methylene chloride was distilled away to give a crude product DL-1-(4′-cyanophenyl)ethylamine. Its conversion rate was 100% based on NMR measurement, with 95% of DL-1-(4′-cyanophenyl)ethylamine, 1% of 1-(4′-cyanophenyl)ethanol, and 4% of other by-products. Since no compound in which reduction of cyano groups occurred was generated, we confirmed that reductive amination reaction was carried out in a functional-group-selective manner.

Workup

  1. distillationAfter distillation of the solvent
  2. additiona saturated sodium hydrogen carbonate solution was added
  3. extractiona product was extracted with methylene chloride
  4. washthe organic layer was washed with water
  5. dry with materialthe product was dried with sodium sulfate
  6. customThe drying agent was removed by filtration
  7. distillationthe methylene chloride was distilled away

Sources & evidence

ORD record
ord-5c5bcb14c95646f1a26f4224e84cb99b
Source dataset
uspto-grants-2013_07
Patent number
US08481735B2

Reaction notes

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