Hydroxylamine → HCID 136337399, compound

HRID 452130Notes

Reaction equation

HRID 452130 reaction equation
[CH2:1]([C:4]1[N:8]([CH2:9][C:10]2[CH:27]=[CH:26][C:13]3/[C:14](=[CH:23]/[C:24]#[N:25])/[C:15]4[CH:22]=[CH:21][CH:20]=[CH:19][C:16]=4[CH2:17][CH2:18][C:12]=3[CH:11]=2)[C:7]2[CH:28]=[CH:29][CH:30]=[CH:31][C:6]=2[N:5]=1)[CH2:2][CH3:3].NO.[N:34]1C=CC=CC=1.[C:40](Cl)(=[O:44])[O:41]CC.C(=O)([O-])O.[Na+].CC(C)([O-])C.[K+]>C(O)C.C(OCC)(=O)C>[CH2:1]([C:4]1[N:8]([CH2:9][C:10]2[CH:27]=[CH:26][C:13]3/[C:14](=[CH:23]/[C:24]4[NH:34][C:40](=[O:44])[O:41][N:25]=4)/[C:15]4[CH:22]=[CH:21][CH:20]=[CH:19][C:16]=4[CH2:17][CH2:18][C:12]=3[CH:11]=2)[C:7]2[CH:28]=[CH:29][CH:30]=[CH:31][C:6]=2[N:5]=1)[CH2:2][CH3:3]

Participants

9

Reactant 6

HCID 787HydroxylamineHCID 1049PyridineHCID 10928Ethyl chloroformateHCID 516892Sodium BicarbonateHCID 23665647Potassium tert-butoxideHCID 67211720HCID 67211720, compound

Product 1

HCID 136337399HCID 136337399, compoundYield 55%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

(E)-[2-(2-Propylbenzimidazol-1-yl)methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene]acetonitrile (467 mg, 1.16 mmol) obtained in Example 1 was dissolved in ethanol (11 mL), hydroxylamine (50% aqueous solution, 2.13 mL, 34.7 mmol) was added, and the mixture was heated under reflux for 16 hr, and concentrated under reduced pressure. The obtained residue was dissolved in DMF (5.5 mL), pyridine (112 μL, 1.39 mmol) and ethyl chlorocarbonate (133 μL, 1.39 mmol) were added at 0° C., and the mixture was stirred at room temperature for 1 hr. Ethyl acetate and saturated aqueous sodium hydrogen carbonate solution were added to the mixture. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was dissolved in toluene (11 mL), potassium tert-butoxide (195 mg, 1.74 mmol) was added, and the mixture was stirred at room temperature for 15 min. Ethyl acetate was added to the mixture, and the organic layer was washed with 5% aqueous citric acid solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform/methanol=99/1) to give the title compound (compound 5) (295 mg, 55%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 16 hr
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe obtained residue was dissolved in DMF (5.5 mL)
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. dissolutionThe obtained residue was dissolved in toluene (11 mL)
  9. stirringthe mixture was stirred at room temperature for 15 min
  10. washthe organic layer was washed with 5% aqueous citric acid solution
  11. dry with materialdried over anhydrous magnesium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customThe residue was purified by silica gel column chromatography (chloroform/methanol=99/1)

Sources & evidence

ORD record
ord-830c81fdb19f44a1b3fef8f2622e4055
Source dataset
uspto-grants-2013_07
Patent number
US08486980B2

Reaction notes

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