potassium (1Z)-1-[2-(dibenzylamino)-3-nitropyridin-4-yl]-3-ethoxy-3-oxoprop-1-en-2-olate → HCID 68982508, compound

HRID 1821809Notes

Reaction equation

HRID 1821809 reaction equation
[CH2:1]([N:8]([CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:9]1[C:14]([N+:15]([O-])=O)=[C:13](/[CH:18]=[C:19](\[O-])/[C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:12]=[CH:11][N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[K+]>C(O)(=O)C.[Fe]>[CH2:26]([N:8]([CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:9]1[N:10]=[CH:11][CH:12]=[C:13]2[CH:18]=[C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[NH:15][C:14]=12)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

4

Reactant 1

HCID 86619020potassium (1Z)-1-[2-(dibenzylamino)-3-nitropyridin-4-yl]-3-ethoxy-3-oxoprop-1-en-2-olate

Product 1

HCID 68982508HCID 68982508, compoundYield 68%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
60 °C

Procedure

Potassium (1Z)-1-[2-(dibenzylamino)-3-nitropyridin-4-yl]-3-ethoxy-3-oxoprop-1-en-2-olate (1.63 g, 3.46 mmol) was dissolved in glacial acetic acid (21 mL) and treated with iron powder (851 mg, 15.2 mmol). This mixture was warmed to 60° C. for 3.5 h and cooled to room temperature. The slurry was filtered through diatomaceous earth to remove the catalyst, and the filtrate was concentrated in vacuo. The residue was purified by chromatography (silica gel, gradient 0-50% ethyl acetate/dichloromethane) to provide ethyl 7-(dibenzylamino)-1H-pyrrolo[2,3-c]pyridine-2-carboxylate (902 mg, 68%) as a tan solid: Rf 0.55 (silica gel, 67:33 hexanes/ethyl acetate); mp 120-123° C.; 1H NMR (300 MHz, CDCl3) δ1.27 (3H, t, J=7.1 Hz), 4.28 (2H, q, J=7.0 Hz), 4.91 (4H, s), 7.03 (1H, J=5.9 Hz), 7.06 (1H, d, J=1.8 Hz), 7.27-7.38 (10H, m), 7.89 (1H, d, J=5.7 Hz), 8.67 (1H, br s); APCI MS m/z 386 [C24H23N3O2+H]+; HPLC (Method A) >99% (AUC), tR=17.7 min.

Workup

  1. temperaturecooled to room temperature
  2. filtrationThe slurry was filtered through diatomaceous earth
  3. customto remove the catalyst
  4. concentrationthe filtrate was concentrated in vacuo
  5. customThe residue was purified by chromatography (silica gel, gradient 0-50% ethyl acetate/dichloromethane)

Sources & evidence

ORD record
ord-dde48a12d527461099a90e44a9763b0f
Source dataset
uspto-grants-2009_10
Patent number
US07608627B2

Reaction notes

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