HCID 69849039, compound → HCID 60060171, compound

HRID 1838310Notes

Reaction equation

HRID 1838310 reaction equation
[CH2:1]([O:3][C:4](=[O:27])[C:5]([C:10]1[C:15]([N+:16]([O-])=O)=[CH:14][CH:13]=[C:12]([O:19][CH:20]2[CH2:25][CH2:24][N:23]([CH3:26])[CH2:22][CH2:21]2)[N:11]=1)=[CH:6]N(C)C)[CH3:2].[H][H]>CCO.[Ni]>[CH2:1]([O:3][C:4]([C:5]1[C:10]2=[N:11][C:12]([O:19][CH:20]3[CH2:25][CH2:24][N:23]([CH3:26])[CH2:22][CH2:21]3)=[CH:13][CH:14]=[C:15]2[NH:16][CH:6]=1)=[O:27])[CH3:2]

Participants

5

Reactant 2

HCID 69849039HCID 69849039, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 60060171HCID 60060171, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

A mixture of 3-dimethylamino-2-[6-(1-methyl-piperidin-4-yloxy)-3-nitro-pyridin-2-yl]-acrylic acid ethyl ester (3.69 g, 9.76 mmol), RANEY 2400 nickel (3.7 g wet) in EtOH (100 mL) is shaken at room temperature under an atmosphere of hydrogen (50 psi) for a period of 7 h. During this time period, the pressure dropped to 20 psi. The reaction vessel is recharged with hydrogen (50 psi) and shaken at room temperature for a period of 17 h. The reaction mixture is filtered through celite and the filtrate washed with EtOH (300 mL) taking care to never allow the filtrate to become dry. The filtrate is concentrated and purified by chromatography on silica (gradient elution with 10% MeOH/CHCl3 with 0.1% NH4OH to 14% MeOH/CHCl3 with 0.1% NH4OH) to give the title compound as a yellow solid: m.p=231.9° C.; 1H NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.64 (d, 1H, J=8.7 Hz), 6.51 (d, 1H, J=8.7 Hz), 5.36-5.28 (m, 1H), 4.26 (q, 2H, J=7.1 Hz), 3.15-3.06 (m, 2H), 3.00-2.90 (m, 2H), 2.61 (s, 3H), 2.30-2.20 (m, 2H), 2.18-2.08 (m, 2H), 1.30 (t, 3H, J−7.1 Hz); 13C NMR (100 MHz, CDCl3) δ 165.0, 159.3, 140.5, 133.7, 125.8, 123.7, 107.3, 106.6, 66.1, 60.0, 51.6, 44.2, 28.5, 14.6; MS (CI) m/z 304.3 (M+1).

Workup

  1. additionDuring this time period, the pressure dropped to 20 psi
  2. stirringshaken at room temperature for a period of 17 h
  3. filtrationThe reaction mixture is filtered through celite
  4. washthe filtrate washed with EtOH (300 mL)
  5. customto become dry
  6. concentrationThe filtrate is concentrated
  7. custompurified by chromatography on silica (gradient elution with 10% MeOH/CHCl3 with 0.1% NH4OH to 14% MeOH/CHCl3 with 0.1% NH4OH)

Sources & evidence

ORD record
ord-3505ab2f730d4378ab3d49da8aee6d2a
Source dataset
uspto-grants-2004_01
Patent number
US06673811B1

Reaction notes

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