Methanol → HCID 67994675, compound

HRID 2361376Notes

Reaction equation

HRID 2361376 reaction equation
Cl[C:2]1[C:7]2[NH:8][C:9]3[CH:10]=[C:11]([O:15][CH2:16][CH2:17][O:18][CH3:19])[CH:12]=[CH:13][C:14]=3[C:6]=2[C:5]([C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-])=O)[C:21]=2[CH3:29])=[N:4][N:3]=1.[C:30]([O-:33])(=[O:32])C.[Na+].[CH3:35]O>CC(N(C)C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:26][C:22]1[C:21]([CH3:29])=[C:20]([C:5]2[C:6]3[C:14]4[CH:13]=[CH:12][C:11]([O:15][CH2:16][CH2:17][O:18][CH3:19])=[CH:10][C:9]=4[NH:8][C:7]=3[C:2]([C:30]([O:33][CH3:35])=[O:32])=[N:3][N:4]=2)[CH:25]=[CH:24][CH:23]=1

Participants

7

Reactant 3

HCID 887MethanolHCID 517045Sodium AcetateHCID 86681525HCID 86681525, compound

Product 1

HCID 67994675HCID 67994675, compoundYield 104%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
90 °C

Procedure

A steel bomb containing a solution of 4-chloro-7-(2-methoxyethoxy)-1-(2-methyl-3-nitrophenyl)-5H-pyridazino[4,5-b]indole (0.5862 g, 1.420 mmol), DPPF (0.118 g, 0.213 mmol), palladium(II) acetate (0.048 g, 0.213 mmol) and sodium acetate (0.233 g, 2.84 mmol) in DMA (10 mL) and methanol (20 mL, 494 mmol) was evacuated and flushed with nitrogen twice. It was then evacuated, filled with CO (g) to 70 psi and heated at 90° C. overnight. The oil bath was removed, and the bomb was cooled to room temperature followed by immersion in dry ice; valve was then released. The cold bath was removed, and the reaction was warmed to room temperature. The solution was filtered through a pad of CELITE® and rinsed with MeOH. The filtrate was concentrated in vacuo, diluted with EtOAc (200 mL) and saturated aqueous NaHCO3 (40 mL). After separation of the layers, the organic layer was washed with brine (40 mL), dried over MgSO4, and concentrated in vacuo to give the desired product (0.600 g, 1.476 mmol, 104% yield) as a light burgundy solid.

Workup

  1. customwas evacuated
  2. customflushed with nitrogen twice
  3. customIt was then evacuated
  4. additionfilled with CO (g) to 70 psi
  5. customThe oil bath was removed
  6. temperaturethe bomb was cooled to room temperature
  7. customvalve was then released
  8. customThe cold bath was removed
  9. temperaturethe reaction was warmed to room temperature
  10. filtrationThe solution was filtered through a pad of CELITE®
  11. washrinsed with MeOH
  12. concentrationThe filtrate was concentrated in vacuo
  13. additiondiluted with EtOAc (200 mL) and saturated aqueous NaHCO3 (40 mL)
  14. customAfter separation of the layers
  15. washthe organic layer was washed with brine (40 mL)
  16. dry with materialdried over MgSO4
  17. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-62e2ed44059d4beb927429db5ca19d00
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

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