Tert-Butyl nitrite → HCID 86644440, compound

HRID 2404514Notes

Reaction equation

HRID 2404514 reaction equation
N[C:2]1[N:6]([C:7]2[CH:12]=[C:11]([S:13][CH2:14][C:15]([F:18])([F:17])[F:16])[C:10]([CH3:19])=[CH:9][C:8]=2[F:20])[N:5]=[C:4]([O:21][C:22]([F:31])([F:30])[CH:23]([F:29])[O:24][C:25]([F:28])([F:27])[F:26])[C:3]=1[Cl:32].N(OC(C)(C)C)=O>O1CCCC1>[Cl:32][C:3]1[C:4]([O:21][C:22]([F:31])([F:30])[CH:23]([F:29])[O:24][C:25]([F:26])([F:27])[F:28])=[N:5][N:6]([C:7]2[CH:12]=[C:11]([S:13][CH2:14][C:15]([F:18])([F:17])[F:16])[C:10]([CH3:19])=[CH:9][C:8]=2[F:20])[CH:2]=1

Participants

4

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 86644437HCID 86644437, compound

Product 1

HCID 86644440HCID 86644440, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

0.9 g of 5-amino-1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-{1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy}pyrazole was dissolved in 30 mL of acetonitrile, and 0.27 g of N-chlorosuccinimide was added under cooling with ice. After stirring for 10 minutes under cooling with ice, the solvent was distilled off under reduced pressure, extraction with ethyl acetate was carried out, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:4) to obtain 5-amino-4-chloro-1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-{1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy}pyrazole. Then, the obtained pyrazole derivative was dissolved in 30 mL of tetrahydrofuran, and 0.3 mL of t-butyl nitrite was added under cooling with ice. After stirring at room temperature for 12 hours, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate:hexane=1:10) to obtain 0.75 of 4-chloro-1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-{1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy}pyrazole.

Workup

  1. temperatureunder cooling with ice
  2. distillationthe solvent was distilled off under reduced pressure
  3. customthe obtained residue was purified by column chromatography (ethyl acetate:hexane=1:10)

Sources & evidence

ORD record
ord-6eac0a337703480f9941cb8f96325705
Source dataset
uspto-grants-2014_08
Patent number
US08802713B2

Reaction notes

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