Sulfur Dioxide → HCID 19434127, compound

HRID 1735995Notes

Reaction equation

HRID 1735995 reaction equation
C(OC([O:6][CH:7]1[C:12]2[CH:13]=[CH:14][S:15][C:11]=2[S:10](=[O:17])(=[O:16])[N:9]([CH2:18][CH2:19][CH2:20][O:21][CH2:22][CH3:23])[CH2:8]1)C)C.C([Li])CCC.[S:29](=[O:31])=[O:30].O.O.O.C([O-])(=O)C.[Na+].[NH2:40]OS(O)(=O)=O>C1COCC1.O>[CH2:22]([O:21][CH2:20][CH2:19][CH2:18][N:9]1[CH2:8][CH:7]([OH:6])[C:12]2[CH:13]=[C:14]([S:29]([NH2:40])(=[O:31])=[O:30])[S:15][C:11]=2[S:10]1(=[O:17])=[O:16])[CH3:23]

Participants

8

Reactant 5

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 19434130HCID 19434130, compoundHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Product 1

HCID 19434127HCID 19434127, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-60 °C

Procedure

A solution of the product from Step C (13.25 g, 36.5 mmol) in THF (250 mL) was degassed under nitrogen and cooled to -60° C. in a dry-ice/isopropanol bath. n-Butyllithium (16.0 mL of a 2.5M solution, 40 mmol) was added slowly over 5 min and the mixture was stirred at -60° C. for 45 min followed by the introduction of excess sulfur dioxide gas into the flask. The mixture was allowed to warm to room temperature over two hours and the solvent was removed by evaporation. The residue was mixed with water (200 mL) and sodium acetate trihydrate (13.91 g, 102.2 mmol) followed by the addition of hydroxylamine-O-sulfonic acid (6,9 g, 61.32 mmol). The mixture was stirred at room temperature for 18 hr and then extracted with ethyl acetate (5×15 mL). The combined extracts were evaporated and the residue dissolved in THF (150 mL), mixed with 2N HCl (10 mL), warmed gently for 1 hr and then evaporated to a residue. The residue was mixed with ethyl acetate (100 mL) and water (100 mL). The organic layer was separated, washed with saturated aqueous sodium chloride, dried (MgSO4) and evaporated to a residue which was purified by column chromatography (silica, gradient, 3:1 hexane/ethyl acetate to 7:3 methylene chloride/methanol) to provide a pale yellow solid (11.6 g, 86%): mp 140°-145° C. dec. Analysis. Calculated for C11H18N2O6S3 : C, 35.66; H, 4.90; N, 7.56. Found: C, 35.79; H, 4.80; N, 7.47.

Workup

  1. temperatureto warm to room temperature over two hours
  2. customthe solvent was removed by evaporation
  3. stirringThe mixture was stirred at room temperature for 18 hr
  4. extractionextracted with ethyl acetate (5×15 mL)
  5. customThe combined extracts were evaporated
  6. dissolutionthe residue dissolved in THF (150 mL)
  7. additionmixed with 2N HCl (10 mL)
  8. temperaturewarmed gently for 1 hr
  9. customevaporated to a residue
  10. additionThe residue was mixed with ethyl acetate (100 mL) and water (100 mL)
  11. customThe organic layer was separated
  12. washwashed with saturated aqueous sodium chloride
  13. dry with materialdried (MgSO4)
  14. customevaporated to a residue which
  15. customwas purified by column chromatography (silica, gradient, 3:1 hexane/ethyl acetate to 7:3 methylene chloride/methanol)

Sources & evidence

ORD record
ord-bf450c9d7cdf406dbc603bcccdf48136
Source dataset
uspto-grants-1996_07
Patent number
US05538966

Reaction notes

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