Stannous chloride dihydrate → HCID 23139451, compound

HRID 540579Notes

Reaction equation

HRID 540579 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-943bf820c9f04d28a2a53101e65c3319
Source dataset
uspto-grants-2014_10
Patent number
US08871797B2

Reaction notes

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