Sulfur Dioxide → HCID 19434050, compound

HRID 1736035Notes

Reaction equation

HRID 1736035 reaction equation
C(OC([O:6][CH2:7][CH2:8][CH2:9][CH2:10][N:11]1[C:16]([CH2:17][N:18]2[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)=[CH:15][C:14]2[CH:24]=[CH:25][S:26][C:13]=2[S:12]1(=[O:28])=[O:27])C)C.C([Li])CCC.[S:34](=[O:36])=[O:35].[NH2:37]OS(O)(=O)=O.CC([O-])=O.[Na+].C(=O)(O)[O-].[Na+]>C1COCC1.C(OCC)(=O)C>[OH:6][CH2:7][CH2:8][CH2:9][CH2:10][N:11]1[C:16]([CH2:17][N:18]2[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)=[CH:15][C:14]2[CH:24]=[C:25]([S:34]([NH2:37])(=[O:36])=[O:35])[S:26][C:13]=2[S:12]1(=[O:28])=[O:27]

Participants

9

Reactant 6

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 516892Sodium Bicarbonate2×HCID 517045Sodium AcetateHCID 19434133HCID 19434133, compoundHCID 178418339Butyllithium

Product 1

HCID 19434050HCID 19434050, compoundYield 69%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the product from Step D (3.22 g, 7.49 mmol) in anhydrous THF (30 mL) under nitrogen at -70° C. was added n-butyllithium (2.5M in hexanes, 3.30 mL, 8.24 mmol) via syringe over 5 min. The mixture was stirred for 30 min at which point a stream of sulfur dioxide was passed over the surface of the reaction mixture for about 5 min. The mixture was warmed to ambient temperature, evaporated to dryness and the residue was mixed with water (100 mL), cooled on an ice bath at which point hydroxylamine-O-sulfonic acid (1.69 g, 14.9 mmol) and NaOAc (4.07 g, 29.9 mmol) were added; after stirring for 5 min, a saturated solution of sodium bicarbonate (20 mL) was added. The reaction mixture was allowed to warm to ambient temperature and stirred for 16 hr followed by mixing with a saturated solution of sodium bicarbonate (50 mL) and extraction with ethyl acetate (2×200 mL). The combined extracts were washed with 2N HCl (100 mL). The aqueous layer was separated, stirred for 30 min, adjusted to pH 7 by the addition of potassium carbonate, and extracted with ethyl acetate (2×100 mL). The combined extracts were dried (MgSO4), evaporated to dryness and purified by column chromatography (silica, ethyl acetate to 10% ethanol/ethyl acetate, gradient) to give an oil (2.25 g, 69%).

Workup

  1. customevaporated to dryness
  2. additionthe residue was mixed with water (100 mL)
  3. additionwere added
  4. temperatureto warm to ambient temperature
  5. stirringstirred for 16 hr
  6. washThe combined extracts were washed with 2N HCl (100 mL)
  7. customThe aqueous layer was separated
  8. stirringstirred for 30 min
  9. additionadjusted to pH 7 by the addition of potassium carbonate
  10. extractionextracted with ethyl acetate (2×100 mL)
  11. dry with materialThe combined extracts were dried (MgSO4)
  12. customevaporated to dryness
  13. custompurified by column chromatography (silica, ethyl acetate to 10% ethanol/ethyl acetate, gradient)

Sources & evidence

ORD record
ord-d4fec7d3dd614c10a3281b961cc29be4
Source dataset
uspto-grants-1996_07
Patent number
US05538966

Reaction notes

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