HCID 86619021, compound → HCID 68980500, compound

HRID 1821813Notes

Reaction equation

HRID 1821813 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[CH:14]=[C:13](/[CH:15]=[C:16](\[O-])/[C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([N+:23]([O-])=O)=[CH:11][N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[K+]>C(O)(=O)C.C1(C)C=CC=CC=1.[Fe]>[CH2:26]([N:8]([CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:9]1[CH:14]=[C:13]2[CH:15]=[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[NH:23][C:12]2=[CH:11][N:10]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

5

Reactant 1

HCID 86619021HCID 86619021, compound

Product 1

HCID 68980500HCID 68980500, compoundYield 19.6%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of potassium (1Z)-1-[2-(dibenzylamino)-5-nitropyridin-4-yl]-3-ethoxy-3-oxoprop-1-en-2-olate (5.0 g, 10.6 mmol) in acetic acid (151.4 mL) was added iron powder (2.43 g, 43.5 mmol) under a nitrogen atmosphere. The mixture was warmed to 60° C. and stirred for 2 h. The reaction mixture was filtered through diatomaceous earth, and the filtrate was concentrated to ca. 100 mL in volume. The concentrate was poured into rapidly stirring water (ca. 200 mL). The precipitate was observed. Ethyl acetate (150 mL) was added and the mixture was stirred until the solid was dissolved. The layers were separated, and the aqueous layer was extracted with ethyl acetate (2×). The combined extracts were washed with dilute NaHCO3 and saturated NaCl, and dried over Na2SO4. The solution was dark red. Consequently, activated charcoal (Darco G-60, 1.20 g) was added to the solution. After filtration through diatomaceous earth, the filtrate was concentrated to dryness to afford a dark brown solid. The solid was sonicated in toluene (ca. 75 mL) for 30 min. After standing at room temperature overnight, the solid was collected by filtration and rinsed with toluene to give ethyl 5-(dibenzylamino)-1H-pyrrolo[2,3-c]pyridine-2-carboxylate (0.80 g, 19%) as a yellow solid. Further manipulation of the mother liquors provided additional material (0.19 g, 5%): mp 169-174° C.; 1H NMR (300 MHz, CD3OD) δ1.38 (3H, t, J=7.0 Hz), 4.37 (2H, q, T=7.0 Hz), 4.75 (4H, s), 6.64 (1H, d, J=0.9 Hz), 6.85 (1H, d, J=0.9 Hz), 7.21-7.27 (10H, m), 8.48 (1H, s); ESI MS m/z 386 [C24H23N3O2+H]+; HPLC (Method A) >99% (AUC), tR=20.1 min.

Workup

  1. filtrationThe reaction mixture was filtered through diatomaceous earth
  2. concentrationthe filtrate was concentrated to ca. 100 mL in volume
  3. additionThe concentrate was poured into rapidly stirring water (ca. 200 mL)
  4. additionEthyl acetate (150 mL) was added
  5. stirringthe mixture was stirred until the solid
  6. dissolutionwas dissolved
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted with ethyl acetate (2×)
  9. washThe combined extracts were washed with dilute NaHCO3 and saturated NaCl
  10. dry with materialdried over Na2SO4
  11. additionConsequently, activated charcoal (Darco G-60, 1.20 g) was added to the solution
  12. filtrationAfter filtration through diatomaceous earth
  13. concentrationthe filtrate was concentrated to dryness
  14. customto afford a dark brown solid
  15. waitAfter standing at room temperature overnight
  16. filtrationthe solid was collected by filtration
  17. washrinsed with toluene

Sources & evidence

ORD record
ord-8771213bedd74c4da9ed09b211338567
Source dataset
uspto-grants-2009_10
Patent number
US07608627B2

Reaction notes

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