4-(3-Methoxy-4-nitrophenyl)pyridine → 2-(Methyloxy)-4-(4-piperidinyl)aniline

HRID 419558Notes

Reaction equation

HRID 419558 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:12]2[CH:17]=[CH:16][N:15]=[CH:14][CH:13]=2)[CH:6]=[CH:7][C:8]=1[N+:9]([O-])=O>CC(O)=O.CC(O)C.[Pt]=O>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:12]2[CH2:17][CH2:16][NH:15][CH2:14][CH2:13]2)[CH:6]=[CH:7][C:8]=1[NH2:9]

Participants

5

Reactant 1

HCID 137288334-(3-Methoxy-4-nitrophenyl)pyridine

Product 1

HCID 594529072-(Methyloxy)-4-(4-piperidinyl)anilineYield 12%

Reagents, catalysts & solvents 3

HCID 82844Platinum oxide (PtO)CatalystHCID 176Acetic AcidSolventHCID 3776IsopropanolSolvent2×

Procedure

To 4-[3-(methyloxy)-4-nitrophenyl]pyridine (Example 137, step A) (4.6 g, 20 mmol) in HOAc (20 mL) is added platinum oxide (460 mg, 2 mmol). The reaction was evacuated then refilled with 60 psi H2 gas. The reaction was stirred under a H2 atmosphere for 3 days. The reaction was evacuated and the atmosphere replaced with N2. The solvent was removed under vacuum, and the residue taken up in DCM/MeOH. Silica was added, and the solvent removed under vacuum. Silica gel chromatography provided material which contained product and other impurities. This material was dissolved in iPrOH and allowed to stand overnight. The crystals which formed were collected by decanting off the solvent and rinsing with iPrOH. Obtained the title compound of step A (500 mg, 2.4 mmol, 12%) slightly wet with iPrOH as colorless crystals. 1H NMR (400 MHz, DMSO-d6) δ 6.68-6.60 (m, 3H), 3.83 (s, 3H), 3.71 (br s, 2H), 3.38-3.31 (m, 2H), 2.85-2.75 (m, 2H), 2.59-2.49 (m, 1H), 1.91-1.75 (m, 5H).

Workup

  1. customThe reaction was evacuated
  2. additionthen refilled with 60 psi H2 gas
  3. customThe reaction was evacuated
  4. customThe solvent was removed under vacuum
  5. additionSilica was added
  6. customthe solvent removed under vacuum
  7. customSilica gel chromatography provided material which
  8. waitto stand overnight
  9. customThe crystals which formed
  10. customwere collected
  11. customby decanting off the solvent
  12. washrinsing with iPrOH

Sources & evidence

ORD record
ord-95dc5de5cae743668b3eb387e017d351
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

Loading…