Dimethylformamide → 4-[4-(2-Ethoxy-naphthalen-1-ylmethyl)-3,5-diethyl-pyrazol-1-yl]-3,5-dimethyl-benzaldehyde

HRID 1740111Notes

Reaction equation

HRID 1740111 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N:9]2[C:13]([CH2:14][CH3:15])=[C:12]([CH2:16][C:17]3[C:26]4[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=4)[CH:20]=[CH:19][C:18]=3[O:27][CH2:28][CH3:29])[C:11]([CH2:30][CH3:31])=[N:10]2)=[C:4]([CH3:32])[CH:3]=1.C([Li])CCC.CN(C)[CH:40]=[O:41]>C1COCC1>[CH2:28]([O:27][C:18]1[CH:19]=[CH:20][C:21]2[C:26](=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:17]=1[CH2:16][C:12]1[C:11]([CH2:30][CH3:31])=[N:10][N:9]([C:5]2[C:6]([CH3:8])=[CH:7][C:2]([CH:40]=[O:41])=[CH:3][C:4]=2[CH3:32])[C:13]=1[CH2:14][CH3:15])[CH3:29]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 218373011-(4-bromo-2,6-dimethylphenyl)4-(2-ethoxy-naphthalen-1-ylmethyl)-3,5-diethyl-1H-pyrazoleHCID 178418339Butyllithium

Product 1

HCID 218373184-[4-(2-Ethoxy-naphthalen-1-ylmethyl)-3,5-diethyl-pyrazol-1-yl]-3,5-dimethyl-benzaldehydeYield 112.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1-(4-bromo-2,6-dimethylphenyl)4-(2-ethoxy-naphthalen-1-ylmethyl)-3,5-diethyl-1H-pyrazole (0.400 g, 0.81 mmol) in 2.0 ml anhydrous THF was added dropwise to a dry ice-acetone bath cooled solution of n-butyl lithium (2.5 M solution in hexane, 0.358 ml, 0.90 mmol). After stirring 10 minutes, anhydrous dimethylformamide (0.188 ml, 2.43 mmol) was added. After 30 minutes the cooling bath was removed and the mixture was stirred 1 hour. The reaction was quenched by addition of 0.25 ml of a saturated aqueous ammonium chloride solution. After stirring for 5 minutes, the reaction mixture was well-mixed with ethyl acetate/brine (20 ml of each). The aqueous phase was then twice extracted with equal-volume portions of fresh ethyl acetate. The combined organic extracts were dried over anhydrous sodium sulfate, and concentrated in vacuo to yield an oil (400 mg). Flash chromatography of the entire sample (silica gel, 40 micron mesh; elution with ethyl acetate/hexanes=1:4 in volume) afforded the title compound (100 mg) as an oil.

Workup

  1. customAfter 30 minutes the cooling bath was removed
  2. stirringthe mixture was stirred 1 hour
  3. customThe reaction was quenched by addition of 0.25 ml of a saturated aqueous ammonium chloride solution
  4. stirringAfter stirring for 5 minutes
  5. additionthe reaction mixture was well-mixed with ethyl acetate/brine (20 ml of each)
  6. extractionThe aqueous phase was then twice extracted with equal-volume portions of fresh ethyl acetate
  7. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-add5d8edca0c4be586a8baefbd4da155
Source dataset
uspto-grants-1999_10
Patent number
US05968944

Reaction notes

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