1-Bromo-4-(diethoxymethyl)benzene → 4-[(4-Methyl-3-pyridyl)hydroxymethyl]benzaldehyde diethylacetal

HRID 1680020Notes

Reaction equation

HRID 1680020 reaction equation
[CH2:1]([O:3][CH:4]([O:12][CH2:13][CH3:14])[C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][CH:6]=1)[CH3:2].[Mg].[CH3:16][C:17]1[CH:22]=[CH:21][N:20]=[CH:19][C:18]=1[CH:23]=[O:24]>O1CCCC1>[CH2:1]([O:3][CH:4]([O:12][CH2:13][CH3:14])[C:5]1[CH:10]=[CH:9][C:8]([CH:23]([C:18]2[CH:19]=[N:20][CH:21]=[CH:22][C:17]=2[CH3:16])[OH:24])=[CH:7][CH:6]=1)[CH3:2]

Participants

5

Reactant 3

HCID 6883401-Bromo-4-(diethoxymethyl)benzeneHCID 5462224MagnesiumHCID 124604704-Methylpyridine-3-carbaldehyde

Product 1

HCID 204734154-[(4-Methyl-3-pyridyl)hydroxymethyl]benzaldehyde diethylacetalYield 58.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Under an atmosphere of nitrogen, a solution of 900 mg of 4-bromobenzaldehyde diethylacetal in 1.8 ml of tetrahydrofuran was added dropwise to 83 mg of magnesium at 50° C. to 60° C., and the mixture was stirred at that temperature for 10 minutes, and then diluted with 2 ml of tetrahydrofuran. The solution, thus obtained, was added dropwise to a solution of 280 mg of 4-methyl-3-formylpyridine [prepared as described in J. Org. Chem., 25, 560(1960)]in 7 ml of tetrahydrofuran at 0° C., and the mixture was stirred at the same temperature for one hour. The reaction mixture was quenched with a saturated aqueous solution of ammonium chloride, and concentrated under reduced pressure. To the residue was added a saturated aqueous solution of sodium bicarbonate, and the mixture was extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using a mixture of ethyl acetate and cyclohexane (7:3) as eluent to give 406 mg of the title compound having the following physical characteristics:

Workup

  1. customThe solution, thus obtained
  2. customprepared
  3. customThe reaction mixture was quenched with a saturated aqueous solution of ammonium chloride
  4. concentrationconcentrated under reduced pressure
  5. additionTo the residue was added a saturated aqueous solution of sodium bicarbonate
  6. extractionthe mixture was extracted with ethyl acetate
  7. washThe extract was washed with water
  8. dry with materialdried over magnesium sulphate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by column chromatography on silica gel using
  11. additiona mixture of ethyl acetate and cyclohexane (7:3) as eluent

Sources & evidence

ORD record
ord-6ddd8903f2c6459a86893135184fd6bd
Source dataset
uspto-grants-1981_06
Patent number
US04271170

Reaction notes

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