Sodium borohydride → 2-(Methyloxy)-4-(4-propyl-1-piperazinyl)aniline

HRID 419546Notes

Reaction equation

HRID 419546 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][CH2:19][CH3:20])[CH2:14][CH2:13]2)[CH:6]=[CH:7][C:8]=1[N+:9]([O-])=O.[BH4-].[Na+]>O.O.O.O.O.O.[Ni](Cl)Cl.CO.C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([N:12]2[CH2:13][CH2:14][N:15]([CH2:18][CH2:19][CH3:20])[CH2:16][CH2:17]2)[CH:6]=[CH:7][C:8]=1[NH2:9]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 598602661-[3-(Methyloxy)-4-nitrophenyl]-4-propylpiperazine

Product 1

HCID 598602822-(Methyloxy)-4-(4-propyl-1-piperazinyl)anilineYield 93.2%

Reagents, catalysts & solvents 2

HCID 11791229Dichloronickel;hexahydrateCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

A mixture of 1-[3-(methyloxy)-4-nitrophenyl]-4-propylpiperazine (0.204 g, 0.73 mmol) and nickel(II) chloride hexahydrate (0.087 g, 0.37 mmol) was stirred in 2:1 MeOH/THF (7 mL) under N2 at rt. To this mixture was added NaBH4 (0.097 g, 2.6 mmol) in 2 equal portions over 5 min. The reaction was stirred at rt for about 45 min, then concentrated under vacuum. The residue was dissolved in DCM and poured through Celite, washing with DCM and EtOAc. The filtrate was concentrated and chromatographed on silica gel to give the title compound of step B (170 mg, 0.68 mmol, 93%) as a grey oil. 1H NMR (400 MHz, DMSO-d6): δ 6.50 (d, 1H, J=8.25), 6.47 (d, 1H, J=2.38 Hz), 6.26 (dd, 1H, J=2.47 and 8.34 Hz), 4.19 (br s, 2H), 3.72 (s, 3H), 2.90-2.94 (m, 4H), 2.43-2.47 (m, 4H), 2.25 (t, 2H, J=7.42 Hz), 1.44 (q, 2H, J=7.39 Hz), 0.86 (t, 3H, J=7.33 Hz).

Workup

  1. concentrationconcentrated under vacuum
  2. dissolutionThe residue was dissolved in DCM
  3. additionpoured through Celite
  4. washwashing with DCM and EtOAc
  5. concentrationThe filtrate was concentrated
  6. customchromatographed on silica gel

Sources & evidence

ORD record
ord-e2d9e258f36c416592c274de253c04f0
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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