291756-82-6 → HCID 68156814, compound

HRID 1520801Notes

Reaction equation

HRID 1520801 reaction equation
F[P-](F)(F)(F)(F)F.[CH3:8][N:9](C)/[CH:10]=[C:11](\[C:16]([F:19])([F:18])[F:17])/[CH:12]=[N+:13](C)C.Cl.[Br:22][C:23]1[CH:28]=[C:27](C)[C:26](NN)=[C:25]([CH3:32])[CH:24]=1.C[O-].[Na+]>O1CCCC1>[Br:22][C:23]1[CH:28]=[C:27]([CH3:26])[C:8]([N:9]2[CH:10]=[C:11]([C:16]([F:19])([F:18])[F:17])[CH:12]=[N:13]2)=[C:25]([CH3:32])[CH:24]=1

Participants

5

Reactant 3

HCID 10545080291756-82-6HCID 10942334Sodium MethoxideHCID 21837319(4-bromo-2,6-dimethylphenyl)hydrazinehydrochloride

Product 1

HCID 68156814HCID 68156814, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

(Z)—N-(3-(dimethylamino)-2-(trifluoromethyl)allylidene)-N-methyl methanaminium hexafluorophosphate (3000 mg, 8.819 mmol) and 1-(4-bromo-2,6-dimethylphenyl)hydrazine hydrochloride (2480 mg, 9.84 mmol) were suspended in tetrahydrofuran. The suspension was cooled to 0° C. Sodium methoxide (551 mg, 9.7 mmol) was added as a solid in one portion. The ice bath was removed and the mixture warmed to room temperature and stirred for 48 hours. Trifluoroacetic acid (3 mL) was then added at room temperature. The reaction was heated to 80° C. for 5 hours, diluted with ethyl acetate and washed with saturated sodium bicarbonate twice. The combined aqueous washings were extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated. Purification by column chromatography (0-20% ethyl acetate in heptane), gave 1-(4-bromo-2,6-dimethylphenyl)-4-(trifluoromethyl)-1H-pyrazole as an oil. 1H NMR (400 MHz, CDCl3, δ): 7.93 (s, 1H), 7.71 (s, 1H), 7.31 (s, 2H), 1.99 (s, 6H).

Workup

  1. customThe ice bath was removed
  2. temperaturethe mixture warmed to room temperature
  3. additionTrifluoroacetic acid (3 mL) was then added at room temperature
  4. temperatureThe reaction was heated to 80° C. for 5 hours
  5. additiondiluted with ethyl acetate
  6. washwashed with saturated sodium bicarbonate twice
  7. extractionThe combined aqueous washings were extracted with ethyl acetate
  8. washThe combined organic layers were washed with brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by column chromatography (0-20% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-66d8ee40bd8e4df0822633d084f3f7b0
Source dataset
uspto-grants-2015_07
Patent number
US09073871B2

Reaction notes

Loading…