Ammonia → Tert-butyl 4-(4-aminobenzylidene)piperidine-1-carboxylate

HRID 515285Notes

Reaction equation

HRID 515285 reaction equation
F[C:2]1[CH:3]=[C:4]([CH:19]=[CH:20][C:21]=1[N+:22]([O-])=O)[CH:5]=[C:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH2:7]1.N>C(O)C.ClCCl.O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2]>[NH2:22][C:21]1[CH:20]=[CH:19][C:4]([CH:5]=[C:6]2[CH2:7][CH2:8][N:9]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[CH2:10][CH2:11]2)=[CH:3][CH:2]=1

Participants

7

Reactant 2

HCID 222AmmoniaHCID 67192635tert-Butyl 4-(3-fluoro-4-nitrobenzylidene)piperidine-1-carboxylate

Product 1

HCID 67194258Tert-butyl 4-(4-aminobenzylidene)piperidine-1-carboxylateYield 70.1%

Reagents, catalysts & solvents 4

HCID 62662Ferrous sulfate heptahydrateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
85 °C

Procedure

tert-Butyl 4-(3-fluoro-4-nitrobenzylidene)piperidine-1-carboxylate (2.97 mmol, 1 g), iron(II) sulfate heptahydrate (20.42 mmol, 5.68 g) and ammonia (10.02 mmol, 11.39 ml) were combined in ethanol (20 mL) and heated at 85° C. overnight. The reaction mixture was diluted with dichloromethane and water then filtered through celite. The organic phase of the filtrate was dried and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluting with dichloromethane to 3% methanol/dichloromethane) to afford the intermediate tert-butyl 4-(4-aminobenzylidene)piperidine-1-carboxylate (600 mg).

Workup

  1. filtrationthen filtered through celite
  2. customThe organic phase of the filtrate was dried
  3. concentrationconcentrated under reduced pressure
  4. customThe resulting residue was purified by silica gel column chromatography (eluting with dichloromethane to 3% methanol/dichloromethane)

Sources & evidence

ORD record
ord-a53485e6b62e40acbdb64b767f52dcca
Source dataset
uspto-grants-2015_08
Patent number
US09108939B2

Reaction notes

Loading…