Sodium hydride → (1,2-dimethyl-6,7-dihydrocyclopenta[e]indazol-8(2H)-ylidene)acetonitrile

HRID 887762Notes

Reaction equation

HRID 887762 reaction equation
[H-].[Na+].[C:3]([CH2:5]P(=O)(OCC)OCC)#[N:4].[CH3:14][C:15]1[N:16]([CH3:28])[N:17]=[C:18]2[C:23]=1[C:22]1[C:24](=O)[CH2:25][CH2:26][C:21]=1[CH:20]=[CH:19]2>O1CCCC1.C(=O)([O-])O.[Na+]>[CH3:14][C:15]1[N:16]([CH3:28])[N:17]=[C:18]2[C:23]=1[C:22]1[C:24](=[CH:5][C:3]#[N:4])[CH2:25][CH2:26][C:21]=1[CH:20]=[CH:19]2

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 591458521,2-dimethyl-6,7-dihydrocyclopenta[e]indazol-8(2H)-one

Product 1

HCID 68701355(1,2-dimethyl-6,7-dihydrocyclopenta[e]indazol-8(2H)-ylidene)acetonitrileYield 45.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

To a suspension of 60% sodium hydride (58.1 mg, 1.45 mmol) in tetrahydrofuran (4 mL) was added diethyl cyanomethylphosphonate (255 μL, 1.58 mmol), and the mixture was stirred at room temperature for 15 min. A solution of 1,2-dimethyl-6,7-dihydrocyclopenta[e]indazol-8(2H)-one (243 mg, 1.21 mmol) in tetrahydrofuran (8 mL) was added thereto, and the mixture was stirred at 60° C. for 24 hr. The reaction solution was diluted with saturated aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=30/70→80/20) to give the title compound (122 mg) as a mixture with 1,2-dimethyl-6,7-dihydrocyclopenta[e]indazol-8(2H)-one. The obtained title compound was used for the reaction of Reference Example 28 without purification.

Workup

  1. stirringthe mixture was stirred at 60° C. for 24 hr
  2. extractionextracted with ethyl acetate
  3. washwashed with water and saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customthe residue was purified by silica gel column chromatography (ethyl acetate/hexane=30/70→80/20)

Sources & evidence

ORD record
ord-3fd9e97e81e74f54bf5db141d5fa49af
Source dataset
uspto-grants-2012_08
Patent number
US08247429B2

Reaction notes

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