HCID 71678736, compound → HCID 71678737, compound

HRID 60408Notes

Reaction equation

HRID 60408 reaction equation
[C:1]([O:4][C:5]1[C:6]([CH3:23])=[C:7]2[CH2:21][CH2:20][N:19]([CH3:22])[C:8]2=[N:9][C:10]=1[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])(=[O:3])[CH3:2]>C1C=CC=CC=1.[O-2].[O-2].[O-2].[Ni+3].[Ni+3]>[C:1]([O:4][C:5]1[C:6]([CH3:23])=[C:7]2[CH:21]=[CH:20][N:19]([CH3:22])[C:8]2=[N:9][C:10]=1[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])(=[O:3])[CH3:2]

Participants

4

Reactant 1

HCID 71678736HCID 71678736, compound

Product 1

HCID 71678737HCID 71678737, compound

Reagents, catalysts & solvents 2

HCID 10313272Nickel oxide (Ni2O3)CatalystHCID 241BenzeneSolvent

Procedure

To a solution containing 65 mg (0.20 mmol) of 1d in 5 mL of benzene was added 56 mg (0.61 mmol) of nickel peroxide. The reaction was stirred at reflux for 18 h. The reaction mixture was filtered through a silica gel plug and washed with three 25-mL portions of benzene, followed by two 25-mL portions of ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated under diminished pressure. The residue was purified via flash chromatography on a silica gel column (25×1.7 cm). Step gradient elution with 1:10→1:4 ethyl acetate-hexanes as eluent gave 1,4-dimethyl-6-octyl-1H-pyrrolo[2,3-b]pyridin-5-yl acetate (2d) as a colorless oil: yield 50 mg (48%); silica gel TLC Rf 0.29 (3:7 ethyl acetate-hexanes); 1H NMR (CDCl3) δ 0.98 (t, 3H, J=7.2 Hz), 1.35-1.50 (m, 10H), 1.72 (quint, 2H, J=8.0 Hz), 2.11 (s, 3H), 2.38 (s, 3H), 2.52 (t, 2H, J=8.0 Hz), 3.34 (s, 3H), 6.21 (d, 1H, J=3.6 Hz), 6.88 (d, 1H, J=3.6 Hz).

Workup

  1. temperatureat reflux for 18 h
  2. filtrationThe reaction mixture was filtered through a silica gel plug
  3. washwashed with three 25-mL portions of benzene
  4. washThe combined organic layer was washed with brine
  5. dry with materialdried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under diminished pressure
  8. customThe residue was purified via flash chromatography on a silica gel column (25×1.7 cm)
  9. washStep gradient elution with 1:10→1:4 ethyl acetate-hexanes as eluent

Sources & evidence

ORD record
ord-877e9c6f85344e5e906b1a4fc3c02828
Source dataset
uspto-grants-2016_09
Patent number
US09440967B2

Reaction notes

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