Potassium Carbonate → ethyl 9-(cyanomethyl)-2-methyl-8,9-dihydro-7H-cyclopenta[c]pyrazolo[1,5-a]pyridine-1-carboxylate

HRID 887772Notes

Reaction equation

HRID 887772 reaction equation
[CH:1]1[C:6]2[CH:7]([CH2:10][C:11]#[N:12])[CH2:8][CH2:9][C:5]=2[CH:4]=[CH:3][N:2]=1.[NH2:13]OC1C=CC([N+]([O-])=O)=CC=1[N+]([O-])=O.[C:27]([O:32][CH2:33][CH3:34])(=[O:31])[C:28]#[C:29][CH3:30].C(=O)([O-])[O-].[K+].[K+]>C(#N)C.O>[C:11]([CH2:10][CH:7]1[C:6]2[C:1]3[N:2]([N:13]=[C:29]([CH3:30])[C:28]=3[C:27]([O:32][CH2:33][CH3:34])=[O:31])[CH:3]=[CH:4][C:5]=2[CH2:9][CH2:8]1)#[N:12]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 78043Ethyl 2-butynoateHCID 87140O-(2,4-dinitrophenyl)hydroxylamineHCID 591458942-(6,7-dihydro-5H-cyclopenta[c]pyridin-7-yl)acetonitrile

Product 1

HCID 59145857ethyl 9-(cyanomethyl)-2-methyl-8,9-dihydro-7H-cyclopenta[c]pyrazolo[1,5-a]pyridine-1-carboxylateYield 32%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of 6,7-dihydro-5H-cyclopenta[c]pyridin-7-ylacetonitrile (90.0 mg, 0.569 mmol) in acetonitrile (1.0 mL) was added 1-(aminooxy)-2,4-dinitrobenzene (113 mg, 0.567 mmol), and the mixture was stirred at 40° C. for 12 hr. The solvent was evaporated under reduced pressure. The residue was dissolved in dimethylformamide (1.0 mL), ethyl 2-butynoate (80.0 μL, 0.686 mmol) and potassium carbonate (94.4 mg, 0.683 mmol) were added, and the mixture was stirred at room temperature for 4 hr. The reaction solution was diluted with water, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane=10/90→40/60) to give the title compound (51.2 mg, yield 32%).

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. dissolutionThe residue was dissolved in dimethylformamide (1.0 mL)
  3. stirringthe mixture was stirred at room temperature for 4 hr
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe extract was dried over anhydrous sodium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane=10/90→40/60)

Sources & evidence

ORD record
ord-ea0208ed8f49483a86136b1b59d6f117
Source dataset
uspto-grants-2012_08
Patent number
US08247429B2

Reaction notes

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