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

HRID 746849

Reaction equation

HRID 746849 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-dd0f682ced6f4ed090a42bb0c5e3a338
Source dataset
uspto-grants-2008_07
Patent number
US07393957B2

Linked notes

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