Acetic Acid → 1-(3-methoxy-4-nitrophenyl)-N,N-dimethylpiperidin-4-amine

HRID 419375Notes

Reaction equation

HRID 419375 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([N:12]2[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]2)[CH:6]=[CH:7][C:8]=1[N+:9]([O-:11])=[O:10].[CH3:19][NH:20][CH3:21].CC(O)=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.O>[CH3:19][N:20]([CH3:21])[CH:15]1[CH2:16][CH2:17][N:12]([C:5]2[CH:6]=[CH:7][C:8]([N+:9]([O-:11])=[O:10])=[C:3]([O:2][CH3:1])[CH:4]=2)[CH2:13][CH2:14]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 674DimethylamineHCID 5049666Sodium triacetoxyborohydrideHCID 259188571-(3-Methoxy-4-nitrophenyl)piperidin-4-one

Product 1

HCID 574161521-(3-methoxy-4-nitrophenyl)-N,N-dimethylpiperidin-4-amineYield 88%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 962WaterSolvent

Procedure

To a solution of 1-[3-(methyloxy)-4-nitrophenyl]-4-piperidinone (Example 57, step B; 1.41 g, 5.6 mmol) in 50 mL 1,2-dichloroethane was added a solution of dimethylamine (2M in THF, 5.6 mL, 11.2 mmol), HOAc (1.3 mL, 22.4 mmol) and sodium triacetoxyborohydride (1.78 g, 8.4 mmol). When TLC indicated the reaction to be complete, the solution was diluted with H2O and extracted with DCM. The aqueous phase was brought to pH>7 with the addition of saturated NaHCO3. This was extracted twice with DCM and EtOAc. The combined organic phases were dried over MgSO4 and concentrated to give 1.37 g (88%) of the desired product. 1H NMR (400 MHz, DMSO-d6) δ 7.84 (d, J=9.6 Hz, 1H), 6.54 (dd, J=9.4 and 2.2 Hz, 1H), 6.46 (d, J=2.0 Hz, 1H), 3.99 (d, J=13.2 Hz, 1H), 3.87 (s, 3H), 2.96-2.89 (m, 2H), 2.35-2.30 (m, 1H), 2.15 (s, 6H), 1.79 (d, J=11.6 Hz, 2H), 1.42-1.32 (m, 2H).

Workup

  1. customthe reaction
  2. extractionextracted with DCM
  3. additionThe aqueous phase was brought to pH>7 with the addition of saturated NaHCO3
  4. extractionThis was extracted twice with DCM and EtOAc
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-b68c4926d3c54819bcc456a0302d1b36
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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