Ammonium Acetate → Ethyl 4-amino-3-methylpiperidine-1-carboxylate

HRID 1814852Notes

Reaction equation

HRID 1814852 reaction equation
C([O-])(=O)C.[NH4+].[C:6]([N:11]1[CH2:16][CH2:15][C:14](=O)[CH:13]([CH3:18])[CH2:12]1)([O:8][CH2:9][CH3:10])=[O:7].C([BH3-])#[N:20].[Na+]>CO>[NH2:20][CH:14]1[CH2:15][CH2:16][N:11]([C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH2:12][CH:13]1[CH3:18]

Participants

5

Reactant 3

HCID 517165Ammonium AcetateHCID 5003444Sodium cyanoborohydrideHCID 15075657Ethyl 3-methyl-4-oxopiperidine-1-carboxylate

Product 1

HCID 22278886Ethyl 4-amino-3-methylpiperidine-1-carboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

Ammonium acetate (5 g, 64.93 mmol) was added to the stirred solution of 1-carbethoxy-3-methyl-4-piperidone (1.4 g, 7.56 mmol) in methanol (25 ml) and stirring was continued for 3 hr at ambient temperature. The resulting mixture was cooled at 0° C. and sodium cyanoborohydride (0.5 g, 7.93 mmol) was added to it. Cooling was removed after 10 min. and resulting mixture was stirred for 6 hr at ambient temperature. The reaction mixture was concentrated to dryness, triturated with water, acidified with conc. HCl (pH 3˜4) and extracted with ethyl acetate to remove impurities. The aqueous layer was basified with 1 M sodium hydroxide solution (pH˜10) and extracted with ethyl acetate. Ethyl acetate extract was dried (Na2SO4) and concentrated to dryness to furnish 4-amino-1-carbethoxy-3-methylpiperidine. Yield 1.0 g (72%), C9H18N2O2, m/z 187 (M+1), PMR (CDCl3): 0.94 (dd, 3H), 1.22 (m, 1H), 1.26 (t, 3H), 1.6 (m, 1H), 1.82 (m,1H), 2.4 (m,1H), 2.82 (m, 1H), 3.34 (m, 2H), 3.64 (m, 1H) 4.14 (q, 2H).

Workup

  1. temperatureCooling
  2. customwas removed after 10 min.
  3. customresulting mixture
  4. stirringwas stirred for 6 hr at ambient temperature
  5. concentrationThe reaction mixture was concentrated to dryness
  6. customtriturated with water
  7. extractionextracted with ethyl acetate
  8. customto remove impurities
  9. extractionextracted with ethyl acetate
  10. extractionEthyl acetate extract
  11. dry with materialwas dried (Na2SO4)
  12. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-36e8eb27aa644f368a8ac6919b3e26a7
Source dataset
uspto-grants-2005_04
Patent number
US06878713B2

Reaction notes

Loading…