Ammonium Chloride → 1-(4-Amino-phenyl)-piperidine-4-carboxylic acid ethyl ester

HRID 1772627Notes

Reaction equation

HRID 1772627 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]2[CH2:15][CH2:14][CH:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:12][CH2:11]2)=[CH:6][CH:5]=1)([O-])=O.[NH4+].[Cl-]>CO.[Fe]>[NH2:1][C:4]1[CH:9]=[CH:8][C:7]([N:10]2[CH2:11][CH2:12][CH:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:14][CH2:15]2)=[CH:6][CH:5]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 2796870Ethyl 1-(4-nitrophenyl)piperidine-4-carboxylate

Product 1

HCID 27641811-(4-Amino-phenyl)-piperidine-4-carboxylic acid ethyl esterYield 102.2%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 887MethanolSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of compound 18a (15.0 g, 51.2 mmol) in MeOH (100 mL) was added Fe (9.06 g, 162 mmol) and saturated NH4Cl solution (100 mL). The resulting solution was stirred at 80° C. for 5 h. After cooling to rt, the mixture was extracted with EtOAc (200 mL). The organic layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel, eluting with EtOAc/petroleum ether (1:5 v/v) to obtain compound 18b as a black solid (13.0 g, 97% yield). Mass Spectrum (LCMS, ESI pos.): Calcd. for C14H20N2O2: 249.2 (M+H). Found 249.0.

Workup

  1. temperatureAfter cooling to rt
  2. extractionthe mixture was extracted with EtOAc (200 mL)
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by flash column chromatography on silica gel
  7. washeluting with EtOAc/petroleum ether (1:5 v/v)

Sources & evidence

ORD record
ord-0b60d8e341604e9987b4ebe5f6c29319
Source dataset
uspto-grants-2016_02
Patent number
US09249163B2

Reaction notes

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