Formic Acid → HCID 21875923, compound

HRID 1454608Notes

Reaction equation

HRID 1454608 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([CH2:18][CH2:19][OH:20])=[CH:14][CH:13]=2)[C:3]=1[N+:21]([O-])=O.C(N(CC)CC)C.C(O)=O>C(#N)C.[Pd]>[NH2:21][C:3]1[C:4]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([CH2:18][CH2:19][OH:20])=[CH:14][CH:13]=2)=[N:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[CH3:1]

Participants

6

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 21875649HCID 21875649, compound

Product 1

HCID 21875923HCID 21875923, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6342AcetonitrileSolvent2×

Procedure

To a stirred solution of 2-{4-[(4-methyl-3,5-dinitro-2-pyridinyl)amino]phenyl}ethanol (step 1, 4.2 g, 13.1 mmol), triethylamine (9.6 mL, 68.9 mmol), 10% Pd-C (624 mg, 0.59 mmol) in acetonitrile (14 mL) was added dropwise a solution of formic acid (2.3 mL, 61.0 mmol) in acetonitrile (6.2 mL) at 0° C. over a period of 30 min. After stirring at room temperature for 5 h, the mixture was filtered through a pad of Celite, and the filtrate was concentrated. The residue was dissolved in dichloromethane (100 mL). The solution was washed with 1N aqueous NaOH (50 mL), brine (50 mL), dried (MgSO4), and concentrated. Purification by flash column chromatography on silica gel eluting with hexane/ethyl acetate (gradient elution from 1:1 to 1:2) afforded 2.2 g (60%) of the title compound as red crystals: 1H-NMR (CDCl3) δ 8.42 (1H, s), 7.42 (2H, d, J=8.4 Hz), 7.21 (2H, d, J=8.4 Hz), 6.7 (1H, br s), 3.85 (2H, t, J=6.4 Hz), 2.86 (2H, t, J=6.6 Hz), 2.47 (3H, s).

Workup

  1. filtrationthe mixture was filtered through a pad of Celite
  2. concentrationthe filtrate was concentrated
  3. dissolutionThe residue was dissolved in dichloromethane (100 mL)
  4. washThe solution was washed with 1N aqueous NaOH (50 mL), brine (50 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customPurification by flash column chromatography on silica gel eluting with hexane/ethyl acetate (gradient elution from 1:1 to 1:2)

Sources & evidence

ORD record
ord-16d01cdea2ca4a37b4259c3f5a406185
Source dataset
uspto-grants-2009_01
Patent number
US07479564B2

Reaction notes

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