HCID 23139441, compound → HCID 23139522, compound

HRID 407462Notes

Reaction equation

HRID 407462 reaction equation
[Br:1][C:2]1[C:3]([C:19]([F:22])([F:21])[F:20])=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:12]=[C:11]([N+:13]([O-])=O)[CH:10]=[CH:9][C:8]=1[O:16][CH3:17]>CCO>[Br:1][C:2]1[C:3]([C:19]([F:22])([F:20])[F:21])=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:12]=[C:11]([NH2:13])[CH:10]=[CH:9][C:8]=1[O:16][CH3:17]

Participants

3

Reactant 1

HCID 23139441HCID 23139441, compound

Product 1

HCID 23139522HCID 23139522, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a stirred solution of 4-bromo-5-(2-methoxy-5-nitro-phenyl)-1-methyl-3-trifluoromethyl-1H-pyrazole (0.08 g, 0.20 mmol) in EtOH (0.7 mL) was added SnCl22H2O (0.18 g, 0.80 mmol, 4.0 eq.) and the mixture was stirred at reflux for 2 hours followed by the removal of EtOH under vacuum. The resulting solid was dissolved in EtOAc and 1N NaOH was added until the pH was adjusted to 6. The mixture was stirred overnight and filtered through celite. The aqueous phase was extracted with EtOAc (3×50 mL). The combined organic phase was dried over anhydrous MgSO4, filtered and evaporated to give 3-(4-bromo-2-methyl-5-trifluoromethyl-2H-pyrazol-3-yl)-4-methoxy-phenylamine (0.06 g, 0.06 g, 0.17 mmol, 99% yield after two steps) as a white solid: LCMS m/z (%)=350 (M+H79Br, 95), 352 (M+H81Br, 100). 1H NMR (400 MHz, CDCl3) δ: 6.78 (dd, J=14.0, 6.0 Hz, 1H), 6.76 (dd, J=8.0, 4.0 Hz, 1H), 6.54 (d, J=4.0 Hz, 1H), 3.67 (s, 3H), 3.66 (s, 3H) 3.36 (broad s, 2H).

Workup

  1. temperatureat reflux for 2 hours
  2. customfollowed by the removal of EtOH under vacuum
  3. dissolutionThe resulting solid was dissolved in EtOAc
  4. addition1N NaOH was added until the pH
  5. stirringThe mixture was stirred overnight
  6. filtrationfiltered through celite
  7. extractionThe aqueous phase was extracted with EtOAc (3×50 mL)
  8. dry with materialThe combined organic phase was dried over anhydrous MgSO4
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-85e61691d52e43009b1d1f5db8703568
Source dataset
uspto-grants-2014_06
Patent number
US08754238B2

Reaction notes

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