Ammonium Chloride → HCID 68509550, compound

HRID 1715112Notes

Reaction equation

HRID 1715112 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH2:24][CH:25]=[CH2:26])=[O:22])=[CH:17][C:16]=2[N+:27]([O-])=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH4+].[Cl-]>[Zn]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH2:24][CH:25]=[CH2:26])=[O:22])=[CH:17][C:16]=2[NH2:27])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 25517Ammonium ChlorideHCID 68508231HCID 68508231, compound

Product 1

HCID 68509550HCID 68509550, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 23994ZincCatalyst

Procedure

To a stirred suspension of 4-(4-allyloxycarbonyl-2-nitro-phenylamino)-piperidine-1-carboxylic acid tert-butyl ester (20.0 g, 49.33 mmol, 1.0 equiv) and Zn (23.22 g) 0.36 mol, 7.2 equiv) was added a sat. solution of NH4Cl (7.91 g, 0.15 mol, 3.0 equiv) and the reaction mixture heated to reflux. After 45 min, the reaction was cooled, filtered through Celite and concentrated by evaporation under reduced pressure. The filtrate was diluted with water and extracted with dichloromethane (3×200 mL). The combined organic fractions were washed with water, dried over Na2SO4 and concentrated by evaporation under reduced pressure. The brownish solid material was further washed with a mixture of hexane/ethyl acetate (98:2) to yield 15.7 g (85%) of the title product. 1H NMR (400 MHz, DMSO): δ 1.24-1.33 (m, 2H), 1.46 (s, 9H), 1.90-1.94 (m, 2H), 2.88-2.94 (m, 2H), 3.53-3.55 (m, 1H), 3.88-3.95 (m, 2H), 4.68 (d, J=5.2 Hz, 2H), 4.79 (s, 2H), 5.01 (d, J=7.5, 2H), 5.23 (d, J=10.4 Hz, 1H), 5.34 (d, J=17.3 Hz, 1H), 6.00-6.06 (m, 1H), 6.54 (d, J=8.2 Hz, 1H), 7.21 (m, 2H).

Workup

  1. temperaturethe reaction mixture heated to reflux
  2. temperaturethe reaction was cooled
  3. filtrationfiltered through Celite
  4. concentrationconcentrated by evaporation under reduced pressure
  5. additionThe filtrate was diluted with water
  6. extractionextracted with dichloromethane (3×200 mL)
  7. washThe combined organic fractions were washed with water
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated by evaporation under reduced pressure
  10. washThe brownish solid material was further washed with a mixture of hexane/ethyl acetate (98:2)

Sources & evidence

ORD record
ord-3d19dab44d4644ae87f7cfa6ecb8d08f
Source dataset
uspto-grants-2010_09
Patent number
US07799806B2

Reaction notes

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