Sodium Sulfate → 2-(2,6-Dichloro-4-nitrophenyl)-7-fluoro-2H-pyrazolo[4,3-c]pyridine 5-oxide

HRID 626765Notes

Reaction equation

HRID 626765 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([Cl:11])[C:3]=1[N:12]1[CH:21]=[C:15]2[CH:16]=[N:17][CH:18]=[C:19]([F:20])[C:14]2=[N:13]1.ClC1C=CC=C(C(OO)=[O:30])C=1.S([O-])([O-])(=O)=O.[Na+].[Na+]>C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([Cl:11])[C:3]=1[N:12]1[CH:21]=[C:15]2[CH:16]=[N+:17]([O-:30])[CH:18]=[C:19]([F:20])[C:14]2=[N:13]1

Participants

5

Reactant 3

HCID 24436Sodium SulfateHCID 70297m-Chloroperbenzoic acid2×HCID 696718262-(2,6-Dichloro-4-nitrophenyl)-7-fluoro-2H-pyrazolo[4,3-c]pyridine

Product 1

HCID 696716022-(2,6-Dichloro-4-nitrophenyl)-7-fluoro-2H-pyrazolo[4,3-c]pyridine 5-oxideYield 84%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

2-(2,6-Dichloro-4-nitrophenyl)-7-fluoro-2H-pyrazolo[4,3-c]pyridine (4.78 g, 14.62 mmol) was dissolved in DCM (90 mL) and a solution of meta-chloroperbenzoic acid (3.78 g, 21.93 mmol) in DCM (60 mL, which had been pre-dried over anhydrous sodium sulfate and passed through a phase separator), was added at 0° C. The reaction mixture was stirred at 0° C. for 1 hour and then at room temperature for 4 hours. Another portion of meta-chloroperbenzoic acid (1.26 g, 7.30 mmol) in DCM (20 mL, dried as above) was added and the reaction mixture was stirred for a further 1.25 hour at room temperature. The resultant mixture was sequentially washed with saturated aqueous sodium thiosulfate solution, saturated aqueous sodium bicarbonate solution and brine. The combined aqueous extracts were further extracted with DCM and the combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was triturated with diethyl ether (×3) and the solid was collected by filtration and dried under reduced pressure to afford the title compound as a pale yellow solid (4.20 g, 84% yield). 1H NMR (300 MHz, CDCl3): δ 8.64 (d, J=1.4 Hz, 1H), 8.42 (s, 2H), 8.20 (d, J=2.3 Hz, 1H), 8.02 (dd, J=5.4, 1.4 Hz, 1H).

Workup

  1. additionwas added at 0° C
  2. waitat room temperature for 4 hours
  3. stirringthe reaction mixture was stirred for a further 1.25 hour at room temperature
  4. washThe resultant mixture was sequentially washed with saturated aqueous sodium thiosulfate solution, saturated aqueous sodium bicarbonate solution and brine
  5. extractionThe combined aqueous extracts were further extracted with DCM
  6. dry with materialthe combined organic layers were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was triturated with diethyl ether (×3)
  10. filtrationthe solid was collected by filtration
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-800f4efc7bc4415eb36fc6d760075c6b
Source dataset
uspto-grants-2016_04
Patent number
US09309240B2

Reaction notes

Loading…