Sodium hydride → 3-Methoxyphthalonitrile

HRID 1488902Notes

Reaction equation

HRID 1488902 reaction equation
C[Si]([CH2:5][OH:6])(C)C.[H-].[Na+].[N+]([C:12]1[CH:19]=[CH:18][CH:17]=[C:14]([C:15]#[N:16])[C:13]=1[C:20]#[N:21])([O-])=O>CN(C)C=O>[CH3:5][O:6][C:12]1[CH:19]=[CH:18][CH:17]=[C:14]([C:15]#[N:16])[C:13]=1[C:20]#[N:21]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 766921-(Trimethylsilyl)methanolHCID 1626521,2-Benzenedicarbonitrile, 3-nitro-

Product 1

HCID 109207773-MethoxyphthalonitrileYield 1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
5 °C

Procedure

In 60 ml of N,N-dimethylformamide were dissolved 20 g of trimethylsilylmethanol. This was maintained at 5° C. in a water bath and 4.6 g of sodium hydride were added thereto in the atmosphere of argon. The resulting mixture was stirred at 5° C. for 1 hour. Thereafter, 33.3 g of 3-nitrophthalonitrile dissolved in 160 ml of N,N-dimethylformamide were added dropwise to the mixture. After completion of the addition, the ice bath was removed and the mixture was stirred at room temperature for 24 hours. The reaction product was then added with 200 ml of dilute hydrochloric acid and extracted with 1 liter of toluene. The organic layer was washed well with water, followed by the removal of water with magnesium sulfate and the purification with a toluene/silica gel column. However, the desired compound shown by the above formula (XV) was hardly obtained. The yield was about 1% and 3-methoxyphthalonitrile as a by-product was yielded in an amount of several times that of the compound (XV).

Workup

  1. additionwere added dropwise to the mixture
  2. additionAfter completion of the addition
  3. customthe ice bath was removed
  4. stirringthe mixture was stirred at room temperature for 24 hours
  5. additionThe reaction product was then added with 200 ml of dilute hydrochloric acid
  6. extractionextracted with 1 liter of toluene
  7. washThe organic layer was washed well with water
  8. customfollowed by the removal of water with magnesium sulfate
  9. customthe purification with a toluene/silica gel column
  10. customwas hardly obtained

Sources & evidence

ORD record
ord-03f26aaa3402433ea012272b72258c34
Source dataset
uspto-grants-1997_10
Patent number
US05677025

Reaction notes

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