Methanol → HCID 178422436, compound

HRID 1890335Notes

Reaction equation

HRID 1890335 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[N:14]=[C:13]([OH:15])[CH:12]=[CH:11][C:10]=2[N+:16]([O-])=O)=[C:4]([CH3:19])[CH:3]=1.[CH3:20]O>[Ni]>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:9]3=[N:14][C:13]([OH:15])=[CH:12][CH:11]=[C:10]3[N:16]=[CH:20]2)=[C:4]([CH3:19])[CH:3]=1

Participants

4

Reactant 2

HCID 887MethanolHCID 178422442HCID 178422442, compound

Product 1

HCID 178422436HCID 178422436, compound

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst2×

Conditions

Temperature
50 °C

Procedure

To a solution of 6-(4-bromo-2-methylphenylamino)-5-nitropyridin-2-ol (4.50 g, 13.9 mmol) in MeOH (30 mL) was added Raney Ni (1.00 g). The mixture was stirred vigorously under H2 atmosphere overnight at which time additional Raney nickel (500 mg) was added. After stirring for an additional 45 h under H2 atmosphere, the mixture was filtered through Celite® and concentrated. The residue was dissolved in THF (20 mL) and trimethoxymethane (25 mL) and trifluoroacetic acid (100 μL) was added. The mixture was heated at 50° C. for 12 h followed by additional heating at 80° C. for 4 h. After cooling to room temperature, the solution was concentrated in vacuo. The residue was purified by HPLC to give the title compound as a white solid (442 mg). LCMS m/z=304.1 [M+H]+; 1H NMR (400 MHz, CDCl3) δ ppm 2.07 (s, 3H), 6.61 (d, J=8.6 Hz, 1H), 7.15 (d, J=8.3 Hz, 1H), 7.48 (dd, J1=8.3, J2=1.9 Hz, 1H), 7.55 (s, 1H), 7.82 (s, 1H), 8.04 (d, J=8.6 Hz, 1H).

Workup

  1. additionwas added
  2. filtrationthe mixture was filtered through Celite®
  3. concentrationconcentrated
  4. dissolutionThe residue was dissolved in THF (20 mL)
  5. additiontrimethoxymethane (25 mL) and trifluoroacetic acid (100 μL) was added
  6. temperatureby additional heating at 80° C. for 4 h
  7. temperatureAfter cooling to room temperature
  8. concentrationthe solution was concentrated in vacuo
  9. customThe residue was purified by HPLC

Sources & evidence

ORD record
ord-7c6773cda03943a389b54f89c58e29b6
Source dataset
uspto-grants-2013_08
Patent number
US08507473B2

Reaction notes

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