1H-Pyrazole, 1-methyl- → 2-(2,5-Dimethylphenoxymethyl)phenyl 1-methylpyrazol-5-yl ketone

HRID 1387334Notes

Reaction equation

HRID 1387334 reaction equation
C([Li])CCC.CCCCCC.[CH3:12][N:13]1[CH:17]=[CH:16][CH:15]=[N:14]1.[CH3:18][C:19]1[CH:35]=[CH:34][C:33]([CH3:36])=[CH:32][C:20]=1[O:21][CH2:22][C:23]1[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=1[C:25](Cl)=[O:26]>C1COCC1.Cl>[CH3:12][N:13]1[C:17]([C:25]([C:24]2[CH:28]=[CH:29][CH:30]=[CH:31][C:23]=2[CH2:22][O:21][C:20]2[CH:32]=[C:33]([CH3:36])[CH:34]=[CH:35][C:19]=2[CH3:18])=[O:26])=[CH:16][CH:15]=[N:14]1

Participants

6

Reactant 3

HCID 702551H-Pyrazole, 1-methyl-HCID 226245992-(2,5-Dimethylphenoxymethyl)benzoyl chlorideHCID 178418244HCID 178418244, compound

Product 1

HCID 226246172-(2,5-Dimethylphenoxymethyl)phenyl 1-methylpyrazol-5-yl ketoneYield 15.6%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

Dichloroethane (20 ml), thionyl chloride (1.31 g, 0.011 mol) and N,N-dimethylformamide (0.1 ml) were added to 2-(2,5-dimethylphenoxymethyl)benzoic acid (2.56 g, 0.01 mol), and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to give crude 2-(2,5-dimethylphenoxymethyl)benzoyl chloride. 1.6M n-butyllithium/n-hexane solution (6.25 ml, 0.01 mol) was added to a mixture of 1-methylpyrazole (0.99 g, 0.012 mol) and THF (10 ml) at −70 to −60° C. over 15 minutes, and then the mixture was stirred at −70° C. to room temperature for 1 hour. The reaction mixture was cooled to −70° C., and a solution of the crude 2-(2,5-dimethylphenoxymethyl)benzoyl chloride in THF (10 ml) was added, and the mixture was stirred at −70° C. for 1 hour. After completion of the reaction, iN hydrochloric acid (100 ml) was added, and the mixture was extracted with ether. The ether layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the residue was purified by silica gel chromatography (ethyl acetate/n-hexane) to give 2-(2,5-dimethylphenoxymethyl)phenyl 1-methylpyrazol-5-yl ketone (0.50 g, 15.6%) as colorless crystals.

Workup

  1. stirringthe mixture was stirred at −70° C. for 1 hour
  2. customAfter completion of the reaction
  3. extractionthe mixture was extracted with ether
  4. dry with materialThe ether layer was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customthe residue was purified by silica gel chromatography (ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-cac0265d566d489bb7c9b4216fe5c8b9
Source dataset
uspto-grants-2001_07
Patent number
US06268312B1

Reaction notes

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