Sodium Thiosulfate → 2-(2,6-Dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine-5-oxide

HRID 626684Notes

Reaction equation

HRID 626684 reaction equation
C1C=C(Cl)C=C(C(OO)=[O:9])C=1.[Cl:12][C:13]1[CH:18]=[C:17]([S:19]([CH3:22])(=[O:21])=[O:20])[CH:16]=[C:15]([Cl:23])[C:14]=1[N:24]1[CH:32]=[C:27]2[CH:28]=[N:29][CH:30]=[CH:31][C:26]2=[N:25]1.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl>[Cl:12][C:13]1[CH:18]=[C:17]([S:19]([CH3:22])(=[O:20])=[O:21])[CH:16]=[C:15]([Cl:23])[C:14]=1[N:24]1[CH:32]=[C:27]2[CH:28]=[N+:29]([O-:9])[CH:30]=[CH:31][C:26]2=[N:25]1

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acid2×HCID 696719202-(2,6-dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine

Product 1

HCID 696715112-(2,6-Dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine-5-oxideYield 81.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

mCPBA (569 mg, 3.3 mmol) was added to a cooled (0° C.) solution of 2-(2,6-dichloro-4-methanesulfonylphenyl)-2H-pyrazolo[4,3-c]pyridine (752 mg, 2.2 mmol) in DCM (20 mL) under nitrogen. The reaction was stirred for 1 hour, warmed to room temperature, and stirred for an additional 2 hours. Further mCPBA (150 mg) was added and the reaction mixture was stirred at room temperature for 4 hours before adding sodium thiosulfate (aq.). The organic layer was separated, washed with sodium hydrogen carbonate (sat. aq.) and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (5-10% methanol in DCM) to afford the title compound as a white solid (640 mg, 81% yield). 1H NMR (300 MHz, DMSO-d6): δ 8.94 (dd, J=1.8, 0.9 Hz, 1H), 8.88 (d, J=1.0 Hz, 1H), 8.33 (s, 2H), 7.96 (dd, J=7.5, 1.8 Hz, 1H), 7.86 (dt, J=7.5, 1.0 Hz, 1H), 3.48 (s, 3H). LCMS (Method D): RT=2.13 min, m/z: 358 [M+H+].

Workup

  1. stirringstirred for an additional 2 hours
  2. stirringthe reaction mixture was stirred at room temperature for 4 hours
  3. customThe organic layer was separated
  4. washwashed with sodium hydrogen carbonate (sat. aq.) and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel flash chromatography (5-10% methanol in DCM)

Sources & evidence

ORD record
ord-d5abfe17e449454ebf7f2f4deb1062a1
Source dataset
uspto-grants-2016_04
Patent number
US09309240B2

Reaction notes

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