Sulfur Dioxide → HCID 19434071, compound

HRID 1736029Notes

Reaction equation

HRID 1736029 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([N:9]2[C:14]([CH2:15]O)=[CH:13][C:12]3[CH:17]=[CH:18][S:19][C:11]=3[S:10]2(=[O:21])=[O:20])[CH:6]=[CH:7][CH:8]=1.C([Li])CCC.[S:27](=[O:29])=[O:28].[Cl:30]N1C(=O)CCC1=O.[C:38]([NH2:42])([CH3:41])([CH3:40])[CH3:39]>C1COCC1>[Cl:30][CH2:15][C:14]1[N:9]([C:5]2[CH:6]=[CH:7][CH:8]=[C:3]([O:2][CH3:1])[CH:4]=2)[S:10](=[O:21])(=[O:20])[C:11]2[S:19][C:18]([S:27]([NH:42][C:38]([CH3:41])([CH3:40])[CH3:39])(=[O:29])=[O:28])=[CH:17][C:12]=2[CH:13]=1

Participants

7

Reactant 5

HCID 1119Sulfur DioxideHCID 6385Tert-ButylamineHCID 31398ChlorosuccinimideHCID 19434051HCID 19434051, compoundHCID 178418339Butyllithium

Product 1

HCID 19434071HCID 19434071, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of the product from Example 18, Step D (4.81 g, 14.89 mmol) in anhydrous THF (80 mL) under nitrogen at -70° C. was added n-butyllithium (2.5M, 14.89 mL, 37.22 mmol) over 5 min. After stirring for 1 h, 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 and evaporated to a residue which was mixed with methylene chloride (250 mL). This suspension was cooled on an ice bath and N-chlorosuccinimide (6.96 g, 52.1 mmol) was added. The reaction mixture was stirred at ambient temperature for 2 h and t-butylamine (15 mL, 143 mmol) was added; the mixture was evaporated to dryness after 16 h. The residue was mixed with a saturated aqueous solution of sodium bicarbonate (200 mL) and extracted with ethyl acetate (2×200 mL). The combined extracts were dried (MgSO4) and evaporated to give a residue which was purified by column chromatography (silica, 40% ethyl acetate/hexane) to give an oil (4.41 g, 62%):

Workup

  1. customevaporated to a residue which
  2. additionwas mixed with methylene chloride (250 mL)
  3. temperatureThis suspension was cooled on an ice bath
  4. stirringThe reaction mixture was stirred at ambient temperature for 2 h
  5. customthe mixture was evaporated to dryness after 16 h
  6. additionThe residue was mixed with a saturated aqueous solution of sodium bicarbonate (200 mL)
  7. extractionextracted with ethyl acetate (2×200 mL)
  8. dry with materialThe combined extracts were dried (MgSO4)
  9. customevaporated
  10. customto give a residue which
  11. customwas purified by column chromatography (silica, 40% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-2b6e9fdfe61e4cf49239f935169236c0
Source dataset
uspto-grants-1996_07
Patent number
US05538966

Reaction notes

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