Sulfur Dioxide → 3-(2,5,5-Trimethyl-1,3-dioxan-2-yl)thiophene-2-sulfonamide

HRID 1735986Notes

Reaction equation

HRID 1735986 reaction equation
[CH3:1][C:2]1([C:10]2[CH:14]=[CH:13][S:12][CH:11]=2)[O:7][CH2:6][C:5]([CH3:9])([CH3:8])[CH2:4][O:3]1.C([Li])CCC.[S:20](=[O:22])=[O:21].O.O.O.C([O-])(=O)C.[Na+].[NH2:31]OS(O)(=O)=O>CCCCCC.O.C1COCC1>[CH3:1][C:2]1([C:10]2[CH:14]=[CH:13][S:12][C:11]=2[S:20]([NH2:31])(=[O:22])=[O:21])[O:3][CH2:4][C:5]([CH3:8])([CH3:9])[CH2:6][O:7]1

Participants

10

Reactant 5

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 22902024HCID 22902024, compoundHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Product 1

HCID 229019383-(2,5,5-Trimethyl-1,3-dioxan-2-yl)thiophene-2-sulfonamide

Reagents, catalysts & solvents 4

HCID 8058HexaneCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

To a solution of 3-(2,5,5-trimethyl-1,3-dioxan-2-yl)thiophene (106 g, 0.5 mol) in hexane (1200 mL) at -60° C. was added a 2.5M solution of n-butyllithium in hexane (240 mL, 0.6 mmol) over 40 min. The mixture was allowed to warm to room temperature (approximately 1.5 hr) and then once again cooled to -60° C. and anhydrous THF (400 mL) added. Sulfur dioxide was passed over the surface of the reaction mixture for 30 min at which point the reaction mixture was allowed to warm to room temperature under a positive SO2 pressure (approximately 1 hr). The solvent was removed and the residue dissolved in water (1200 mL) to which sodium acetate trihydrate (217.73 g, 1.6 mol) was added. The solution was cooled (ice bath) to 0° C. and hydroxylamine-O-sulfonic acid (107 g, 0.95 mol) was slowly added. The mixture was stirred at room temperature for 18 hr and then extracted with ethyl acetate. The combined extracts were washed with a saturated aqueous sodium bicarbonate solution, brine, dried (Na2SO4) and evaporated to give a viscous brown oil (174.05 g); this product was used in the next step without further purification.

Workup

  1. temperatureonce again cooled to -60° C.
  2. temperatureto warm to room temperature under a positive SO2 pressure (approximately 1 hr)
  3. customThe solvent was removed
  4. additionwas added
  5. temperatureThe solution was cooled (ice bath) to 0° C.
  6. extractionextracted with ethyl acetate
  7. washThe combined extracts were washed with a saturated aqueous sodium bicarbonate solution, brine
  8. dry with materialdried (Na2SO4)
  9. customevaporated

Sources & evidence

ORD record
ord-987f0326a8544d36a1cc6fd9e8d729d2
Source dataset
uspto-grants-1996_07
Patent number
US05538966

Reaction notes

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