Sodium Thiosulfate → Methyl 5-formyl-4-(imidazo[1,2-b]pyridazin-3-yl)thiophene-2-carboxylate

HRID 2046414Notes

Reaction equation

HRID 2046414 reaction equation
[CH:1]([C:3]1[S:7][C:6]([C:8]([O:10][CH3:11])=[O:9])=[CH:5][C:4]=1[C:12]1[N:16]2[N:17]=[CH:18][CH:19]=[CH:20][C:15]2=[N:14][CH:13]=1)=C.C[N+]1([O-])CC[O:25]CC1.S([O-])([O-])(=O)=S.[Na+].[Na+].I([O-])(=O)(=O)=O.[Na+]>C1COCC1.O.O=[Os](=O)(=O)=O>[CH:1]([C:3]1[S:7][C:6]([C:8]([O:10][CH3:11])=[O:9])=[CH:5][C:4]=1[C:12]1[N:16]2[N:17]=[CH:18][CH:19]=[CH:20][C:15]2=[N:14][CH:13]=1)=[O:25]

Participants

8

Reactant 4

HCID 24477Sodium ThiosulfateHCID 82029Methyl morpholine oxide3×HCID 23667635Sodium periodateHCID 58046440HCID 58046440, compound

Product 1

HCID 58046456Methyl 5-formyl-4-(imidazo[1,2-b]pyridazin-3-yl)thiophene-2-carboxylate

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalyst2×HCID 962WaterSolvent4×HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of methyl 5-ethenyl-4-(imidazo[1,2-b]pyridazin-3-yl)thiophene-2-carboxylate (160 mg, 0.56 mmol) in THF (1.9 mL) and water (0.95 mL) were added OsO4 (4% in water, 0.36 mL, 0.056 mmol) and NMO (79 mg, 0.67 mmol). The reaction mixture was left to stir for 5 h, treated with additional 0504 (4% in water, 0.36 mL, 0.056 mmol) and NMO (79 mg, 0.67 mmol), and left to stir overnight. Additional OsO4 (4% in water, 0.36 mL, 0.056 mmol) and NMO (79 mg, 0.67 mmol) were added and the resultant solution was left to stir for 1 d, treated with aqueous sodium thiosulfate, and left to stir for 2 h. The mixture was extracted with dichloromethane (×3). The combined organics were dried (sodium sulfate), and concentrated. The residue was dissolved in THF (6 mL) and water (3 mL), and treated with sodium periodate (143 mg, 0.67 mmol). The mixture was left to stir overnight, diluted with water, and extracted with dichloromethane (×3). The combined organics were dried (sodium sulfate), concentrated, and purified by flash chromatography to afford the title compound as a yellow solid. LRMS (APCI) calc'd for (C13H10N3O3S) [M+H]+, 288.0. found 288.0.

Workup

  1. waitThe reaction mixture was left
  2. waitleft
  3. stirringto stir overnight
  4. stirringto stir for 1 d
  5. waitleft
  6. stirringto stir for 2 h
  7. extractionThe mixture was extracted with dichloromethane (×3)
  8. dry with materialThe combined organics were dried (sodium sulfate)
  9. concentrationconcentrated
  10. dissolutionThe residue was dissolved in THF (6 mL)
  11. waitThe mixture was left
  12. stirringto stir overnight
  13. extractionextracted with dichloromethane (×3)
  14. dry with materialThe combined organics were dried (sodium sulfate)
  15. concentrationconcentrated
  16. custompurified by flash chromatography

Sources & evidence

ORD record
ord-dc79d52859d24e45bd039641c324e726
Source dataset
uspto-grants-2013_11
Patent number
US08592425B2

Reaction notes

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