Hydroxylamine → HCID 178437422, compound

HRID 452133Notes

Reaction equation

HRID 452133 reaction equation
[CH2:1]([C:3]1[N:13]([CH2:14][C:15]2[CH:32]=[CH:31][C:18]3/[C:19](=[CH:28]/[C:29]#[N:30])/[C:20]4[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=4[CH2:22][CH2:23][C:17]=3[CH:16]=2)[C:6]2=[N:7][C:8]([CH3:12])=[CH:9][C:10]([CH3:11])=[C:5]2[N:4]=1)[CH3:2].N[OH:34].C1N=C[N:37]([C:40](N2C=NC=C2)=[S:41])C=1.C1CCN2C(=NCCC2)CC1>C(O)C.C(OCC)(=O)C>[CH2:1]([C:3]1[N:13]([CH2:14][C:15]2[CH:32]=[CH:31][C:18]3/[C:19](=[CH:28]/[C:29]4[NH:37][C:40](=[S:41])[O:34][N:30]=4)/[C:20]4[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=4[CH2:22][CH2:23][C:17]=3[CH:16]=2)[C:6]2=[N:7][C:8]([CH3:12])=[CH:9][C:10]([CH3:11])=[C:5]2[N:4]=1)[CH3:2]

Participants

7

Reactant 4

HCID 787HydroxylamineHCID 802641,1'-ThiocarbonyldiimidazoleHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 22858094(E)-[2-(2-ethyl-5,7-dimethyl-3H-imidazo[4,5-b]pyridin-3-yl)methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene]acetonitrile

Product 1

HCID 178437422HCID 178437422, compoundYield 26%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

(E)-[2-(2-Ethyl-5,7-dimethyl-3H-imidazo[4,5-b]pyridin-3-yl)methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene]acetonitrile (JP-B-2526005; 220 mg, 0.53 mmol) was dissolved in ethanol (5 mL), hydroxylamine (50% aqueous solution, 0.48 mL, 7.63 mmol) was added, and the mixture was heated under reflux for 16 hr, and concentrated under reduced pressure. The obtained residue was dissolved in acetonitrile (5 mL), N,N′-thiocarbonyldiimidazole (141 mg, 0.79 mmol) and DBU (315 μL, 2.11 mmol) were added, and the mixture was stirred at room temperature for 2 hr. 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=95/5) to give the title compound (compound 8) (67 mg, 26%).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 16 hr
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe obtained residue was dissolved in acetonitrile (5 mL)
  5. washthe organic layer was washed with 5% aqueous citric acid solution
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (chloroform/methanol=95/5)

Sources & evidence

ORD record
ord-872e877dcbd0434b809463a8f093fe43
Source dataset
uspto-grants-2013_07
Patent number
US08486980B2

Reaction notes

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