Ethyl Acetate → Butyl 4-((3,4-diaminophenoxy)methyl)piperidine-1-carboxylate

HRID 415101Notes

Reaction equation

HRID 415101 reaction equation
[NH2:1][C:2]1[CH:22]=[CH:21][C:5]([O:6][CH2:7][CH:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])(C)C)=[O:15])[CH2:10][CH2:9]2)=[CH:4][C:3]=1[N+:23]([O-])=O.[H][H].[C:28](OCC)(=O)[CH3:29]>CO.[Pd]>[NH2:23][C:3]1[CH:4]=[C:5]([CH:21]=[CH:22][C:2]=1[NH2:1])[O:6][CH2:7][CH:8]1[CH2:9][CH2:10][N:11]([C:14]([O:16][CH2:17][CH2:20][CH2:28][CH3:29])=[O:15])[CH2:12][CH2:13]1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 59349493Tert-butyl 4-((4-amino-3-nitrophenoxy)methyl)piperidine-1-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 86642035Butyl 4-((3,4-diaminophenoxy)methyl)piperidine-1-carboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

tert-Butyl 4-((4-amino-3-nitrophenoxy)methyl)piperidine-1-carboxylate (3.58 g, 10.18 mmoles,) was dissolved in ethyl acetate (60 ml) and methanol (40 ml). The solution was treated with 600 mg of 10% palladium on carbon (50% water w/w). The slurry was then shaken on a Parr hydrogenator and treated with a 40 psi of hydrogen gas, at room temperature. After 16 hours, the slurry was filtered through a plug of Celite, which was subsequently washed with ethyl acetate (50 ml) and methanol (50 ml). The resulting filtrate was then evaporated at reduced pressure to give 3.42 g of tent-butyl 4-((3,4-diaminophenoxy)methyl)piperidine-1-carboxylate (100% yield). The material was used in the next step without any further purification. 1H-NMR (400 MHz, DMSO-d6) δ 8.40 (s, 1H), 7.49 (d, 1H), 7.24 (d, 1H), 5.32 (br s, 4H), 3.82 (d, 2H), 3.65 (m, 2H), 2.40 (s, 3H), 1.76 (m, 1H), 1.54 (m, 2H), 1.38 (s, 9H), 0.98 (m, 2H). MS (EI): 322 (MH+).

Workup

  1. filtrationthe slurry was filtered through a plug of Celite, which
  2. washwas subsequently washed with ethyl acetate (50 ml) and methanol (50 ml)
  3. customThe resulting filtrate was then evaporated at reduced pressure

Sources & evidence

ORD record
ord-fc327245eb1942d094c51e7373babaab
Source dataset
uspto-grants-2012_01
Patent number
US08088767B2

Reaction notes

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