Hydrochloric Acid → HCID 17862356, compound

HRID 644833Notes

Reaction equation

HRID 644833 reaction equation
C(=O)([O-])[O-].[K+].[K+].[Cl:7][C:8]1[CH:13]=[C:12](Cl)[CH:11]=[CH:10][C:9]=1[N+:15]([O-:17])=[O:16].[OH:18][C:19]1[CH:23]=[C:22]([CH3:24])[NH:21][N:20]=1.Cl>CN(C=O)C>[Cl:7][C:8]1[CH:13]=[C:12]([O:18][C:19]2[CH:23]=[C:22]([CH3:24])[NH:21][N:20]=2)[CH:11]=[CH:10][C:9]=1[N+:15]([O-:17])=[O:16]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 118992,4-DichloronitrobenzeneHCID 3197713H-Pyrazol-3-one, 2,4-dihydro-5-methyl-

Product 1

HCID 17862356HCID 17862356, compoundYield 48.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Potassium carbonate (3.52 g, 25.5 mmol) and 2,4-dichloronitrobenzene (9.79 g, 51.0 mmol) were added to a solution of 3-hydroxy-5-methylpyrazole (5.00 g, 51.0 mmol) in DMF (130 ml) at room temperature, and the mixture was stirred at room temperature overnight. After completion of the reaction, the reaction mixture was poured into 1N hydrochloric acid (200 ml) and extracted with ethyl acetate (100 ml×3). An organic layer was washed with water (100 ml×3), dried over anhydrous magnesium sulfate and filtered to remove magnesium sulfate, and the solvent was distilled off from the filtrate under reduced pressure. The resultant crude product was purified with a silica gel column (ethyl acetate/hexane=1/3), to give a yellow solid of 3-(3-chloro-4-nitrophenyloxy)-5-methylpyrazole (6.33 g, yield: 48.9%) [mp: 91-93° C.; 1H-NMR (CDCl3, TMS, ppm): δ 2.30 (s, 3H), 5.74 (d, J=0.6 Hz, 1H), 7.10 (dd, J=2.8 and 9.1 Hz, 1H), 7.25 (d, J=2.5 Hz, 1H), 7.97 (d, J=9.1 Hz, 1H), 10.73 (br d, J=8.8 Hz, 1H)] and a yellow solid of 3-(5-chloro-2-nitrophenyloxy)-5-methylpyrazole (2.31 g, yield: 17.9%) [mp: 87-90° C.; 1H-NMR (CDCl3, TMS, ppm): δ 2.27 (s, 3H), 5.73 (d, J=0.6 Hz, 1H), 7.17 (dd, J=2.2 and 8.8 Hz, 1H), 7.26 (d, J=2.2 Hz, 1H), 7.91 (d, J=8.8 Hz, 1H), 10.77 (br s, 1H)].

Workup

  1. customAfter completion of the reaction
  2. extractionextracted with ethyl acetate (100 ml×3)
  3. washAn organic layer was washed with water (100 ml×3)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customto remove magnesium sulfate
  7. distillationthe solvent was distilled off from the filtrate under reduced pressure
  8. customThe resultant crude product was purified with a silica gel column (ethyl acetate/hexane=1/3)

Sources & evidence

ORD record
ord-a3c21be16e6e4148b2b9de1621f2f1f7
Source dataset
uspto-grants-2010_04
Patent number
US07700786B2

Reaction notes

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