Sodium hydride → Ammonia

HRID 357619Notes

Reaction equation

HRID 357619 reaction equation
[H-].[Na+].[C:3]([NH:6][N:7]=[CH:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)(=[NH:5])[NH2:4].[CH3:15][O:16][CH:17]([O:20][CH3:21])[CH2:18]Br>CN(C=O)C>[CH:8](=[N:7][NH:6][C:3]([NH:4][CH2:18][CH:17]([O:20][CH3:21])[O:16][CH3:15])=[NH:5])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[NH3:4]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 816722-Bromo-1,1-dimethoxyethaneHCID 178513139HCID 178513139, compound

Product 2

HCID 222AmmoniaHCID 178495984HCID 178495984, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

2.88 g (0.06 mol) of sodium hydride dispersion (approximately 50% in oil; Fluka, Buchs, Switzerland) are added in portions over a period of 10 minutes, with stirring and with the introduction of nitrogen, to a solution of 8.1 g (0.05 mol) of benzaldehyde guanylhydrazone in 80 ml of DMF. After 25 minutes stirring at room temperature, 7.1 ml (0.06 mol) of bromoacetaldehyde dimethylacetal (Aldrich, Buchs, Switzerland; 97%, Cat. no. 24,250-0) are added dropwise to the mixture, which has been cooled in an ice-bath. The reaction mixture is stirred for one hour at room temperature and for 20 hours at 55° C., and then concentration by evaporation is carried out in vacuo and the residue is partitioned between ethyl acetate and water. The organic phase is washed with water and brine and is concentrated by evaporation, and the oily residue is purified by flash chromatography on silica gel having a particle size of 0.04-0.063 mm, using ethyl acetate and ethyl acetate/methanol (9:1). Concentration of the product-containing fractions by evaporation yields the title compound in the form of an oil, Rf value=0.80 (silica gel/methylene chloride:methanol:conc. ammonia (40:10:1)), 1H-NMR (DMSO): δ=8.07 (s, 1H); 7.67-7.73 (m, 2H); 7.23-7.40 (m, 3H); 5.93 (bs, 3H); 4.48 (t, 1H); 3.32 (s, 6H); 3.29 (d, 2H).

Workup

  1. addition24,250-0) are added dropwise to the mixture, which
  2. temperaturehas been cooled in an ice-bath
  3. stirringThe reaction mixture is stirred for one hour at room temperature and for 20 hours at 55° C.
  4. concentrationconcentration
  5. customby evaporation
  6. customthe residue is partitioned between ethyl acetate and water
  7. washThe organic phase is washed with water and brine
  8. concentrationis concentrated by evaporation
  9. customthe oily residue is purified by flash chromatography on silica gel having a particle size of 0.04-0.063 mm
  10. customConcentration of the product-containing fractions by evaporation

Sources & evidence

ORD record
ord-c38ccc24f55f47ee8e1e9dd9e861efcb
Source dataset
uspto-grants-1998_11
Patent number
US05840911

Reaction notes

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