Stannous chloride dihydrate → HCID 23139451, compound

HRID 919494Notes

Reaction equation

HRID 919494 reaction equation
[Cl: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].O.O.Cl[Sn]Cl>CCO>[Cl: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

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 23139479HCID 23139479, compound

Product 1

HCID 23139451HCID 23139451, compoundYield 66.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a stirred solution of 4-chloro-5-(2-methoxy-5-nitro-phenyl)-1-methyl-3-trifluoromethyl-1H-pyrazole (0.11 g, 0.33 mmol) in EtOH (1.0 mL) was added SnCl2.2H2O (0.30 g, 1.31 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-chloro-2-methyl-5-trifluoromethyl-2H-pyrazol-3-yl)-4-methoxy-phenylamine (0.067 g, 0.22 mmol, 66% yield after two steps) as a white solid: LCMS m/z (%)=306 (M+H35Cl, 100), 308 (M+H37Cl, 33). 1H NMR (400 MHz, CDCl3) δ: 6.86 (dd, J=14.0, 6.0 Hz, 1H), 6.84 (dd, J=8.0, 4.0 Hz, 1H), 6.63 (d, J=4.0 Hz, 1H), 3.74 (s, 3H), 3.72 (s, 3H).

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-9d7309df292f4fb5a70f866798be51bd
Source dataset
uspto-grants-2016_03
Patent number
US09273035B2

Reaction notes

Loading…