Pyrazole → HCID 58508677, compound

HRID 454518Notes

Reaction equation

HRID 454518 reaction equation
[NH:1]1[CH:5]=[CH:4][CH:3]=[N:2]1.C(=O)([O-])[O-].[K+].[K+].N1CCC[C@@H]1C(O)=O.Br[C:21]1[CH:33]=[CH:32][C:24]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[C:23]([N+:34]([O-:36])=[O:35])[CH:22]=1>[Cu]I.O.C(OCC)(=O)C.CS(C)=O>[N+:34]([C:23]1[CH:22]=[C:21]([N:1]2[CH:5]=[CH:4][CH:3]=[N:2]2)[CH:33]=[CH:32][C:24]=1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])([O-:36])=[O:35]

Participants

9

Reactant 4

HCID 1048PyrazoleHCID 8988D-ProlineHCID 11430Potassium CarbonateHCID 26369829tert-Butyl 4-bromo-2-nitrobenzoate

Product 1

HCID 58508677HCID 58508677, compoundYield 41.8%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

1H-Pyrazole (0.14 g), potassium carbonate (0.46 g), D-proline (38 mg), and copper(I) iodide (32 mg) were added to a dimethyl sulfoxide (5 mL) solution of tert-butyl 4-bromo-2-nitrobenzoate (0.50 g), followed by stirring under a nitrogen atmosphere at 100° C. for 3 hours. After cooling the reaction mixture to room temperature, ethyl acetate and water were added thereto, and the insoluble substance was removed by filtration. The organic layer was separated, washed with water and a saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 100-80% hexane/ethyl acetate] to obtain 0.20 g of tert-butyl 2-nitro-4-(1H-pyrazol-1-yl)benzoate as a white solid.

Workup

  1. temperatureAfter cooling the reaction mixture to room temperature
  2. customthe insoluble substance was removed by filtration
  3. customThe organic layer was separated
  4. washwashed with water
  5. dry with materiala saturated aqueous solution of sodium chloride sequentially, and dried over anhydrous magnesium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe obtained residue was purified by silica gel column chromatography [Fuji Silysia Chemical Ltd., PSQ100B (spherical), eluent: 100-80% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-51adc1a33f634014a5efd964de06bad5
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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