Acetic Acid → Ethyl 4-(1-amino-2-methylpropyl)benzoate

HRID 1049088Notes

Reaction equation

HRID 1049088 reaction equation
O[N:2]=[C:3]([C:7]1[CH:17]=[CH:16][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:9][CH:8]=1)[CH:4]([CH3:6])[CH3:5].C(O)(=O)C.[OH-].[NH4+].C(Cl)Cl>[Zn].CCOC(C)=O>[NH2:2][CH:3]([C:7]1[CH:17]=[CH:16][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:9][CH:8]=1)[CH:4]([CH3:5])[CH3:6]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6344DichloromethaneHCID 14923Ammonium HydroxideHCID 76779939Ethyl 4-(1-(hydroxyimino)-2-methylpropyl)benzoate

Product 1

HCID 58417523Ethyl 4-(1-amino-2-methylpropyl)benzoateYield 55%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To the crude ethyl 4-(1-(hydroxyimino)-2-methylpropyl)benzoate in a 100-mL round-bottom flask was added acetic acid (8 mL) and zinc dust (1.33 g, 20.3 mmol). The mixture was stirred at rt for 1 h, then filtered through a pad of Celite. The pad was rinsed with ethanol (50 mL). Combined filtrate was concentrated to give a solid. To the solid residue was added ammonium hydroxide (20 mL) and DCM (50 mL). The solution was stirred at rt for 10 min. After separation, the aqueous layer was extracted with DCM (2×50 mL). Combined organic phases were washed with brine, dried (MgSO4), and concentrated to give an oil. Flash column chromatography (EtOAc:hexanes:TEA, 20:80:2 to 100:0:2) afforded ethyl 4-(1-amino-2-methylpropyl)benzoate (0.563 g, 55%) as a clear oil. LC-MS: (FA) ES+ 222; 1H NMR (CDCl3, 300 MHz) δ7.99 (d, J=8.3 Hz, 2H), 7.36 (d, J=8.5 Hz, 2H), 4.37 (q, J=7.2 Hz, 2 μl), 3.68 (d, J=7.0 Hz, 1H), 1.86 (m, 1H), 1.39 (t, J=7.0 Hz, 3H), 0.96 (d, J=7.0 Hz, 3H), 0.77 (d, J=7.0 Hz, 3H).

Workup

  1. filtrationfiltered through a pad of Celite
  2. washThe pad was rinsed with ethanol (50 mL)
  3. concentrationCombined filtrate was concentrated
  4. customto give a solid
  5. stirringThe solution was stirred at rt for 10 min
  6. customAfter separation
  7. extractionthe aqueous layer was extracted with DCM (2×50 mL)
  8. washCombined organic phases were washed with brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. customto give an oil

Sources & evidence

ORD record
ord-041c685f2ea44ec8b4bddb7819e5fbad
Source dataset
uspto-grants-2016_07
Patent number
US09382197B2

Reaction notes

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