Ethanol → Carbamic acid, N-[1-(4-aminophenyl)-4-piperidinyl]-, 1,1-dimethylethyl ester

HRID 1485208Notes

Reaction equation

HRID 1485208 reaction equation
[C:1]([O:5][C:6](=[O:23])[NH:7][CH:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-])=O)=[CH:16][CH:15]=2)[CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2].CCO.[H][H]>CN(C=O)C.CCOC(C)=O.[Pd]>[C:1]([O:5][C:6](=[O:23])[NH:7][CH:8]1[CH2:9][CH2:10][N:11]([C:14]2[CH:15]=[CH:16][C:17]([NH2:20])=[CH:18][CH:19]=2)[CH2:12][CH2:13]1)([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 3

HCID 702EthanolHCID 12050748HCID 12050748, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 12050749Carbamic acid, N-[1-(4-aminophenyl)-4-piperidinyl]-, 1,1-dimethylethyl ester

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

tert-Butyl(1-(4-nitrophenyl)piperidin-4-yl)carbamate (I74) (1.038 g, 3.230 mmol) was dissolved in dry DMF (15 mL), EtOAc (15 mL) and absolute EtOH (15 mL) under an atmosphere of nitrogen. 10% Pd/C (0.200 g) in EtOAc (5 mL) was added to the solution and the atmosphere was changed to hydrogen gas (balloon). The reaction was sealed with balloon and stirred at room temperature for 18 hours. The catalyst was removed by filtration through celite, which was washed with EtOAc (5×10 mL). The solvent was removed in vacuo to give a pink solid which was purified by silica gel chromatography using a gradient of 0-80% ethyl acetate in petroleum benzine 40-60° C. to give the title compound (I75) (0.730 g, 78%) as a purple-brown solid; 1H NMR (400 MHz, CDCl3) δ 6.81 (d, J=8.6 Hz, 2H), 6.64 (d, J=8.7 Hz, 2H), 4.55-4.41 (m, 1H), 3.64-3.32 (m, 5H), 2.72 (t, J=11.0 Hz, 2H), 2.08-1.98 (m, 2H), 1.56 (ddd, J=23.7, 11.3, 3.9 Hz, 2H), 1.45 (s, 9H).). LCMS Method C: rt 0.38 min; m/z 292.0 [M+H]+.

Workup

  1. customThe reaction was sealed with balloon
  2. customThe catalyst was removed by filtration through celite, which
  3. washwas washed with EtOAc (5×10 mL)
  4. customThe solvent was removed in vacuo
  5. customto give a pink solid which
  6. customwas purified by silica gel chromatography
  7. customa gradient of 0-80% ethyl acetate in petroleum benzine 40-60° C.

Sources & evidence

ORD record
ord-c8a4eaf2e3dc434c87f81dce3e76c421
Source dataset
uspto-grants-2016_08
Patent number
US09421205B2

Reaction notes

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