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

HRID 465414Notes

Reaction equation

HRID 465414 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

9

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 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 3-(2,5,5-Trimethyl-1,3-dioxane-2-yl)thiophene (2.5 g, 11.7 mmol) in hexane (30 mL) cooled to 0° C. was added via syringe n-butyllithium in hexane (2.5M, 10.3 mL, 25.7 mmol) over 5 min. The mixture was stirred at 0° C. for 20 min, the ice bath was removed and the stirring was continued for 30 min. At this time a white precipitate formed. The mixture was cooled to -60° C. and THF (20 mL) was added. Sulfur dioxide was then passed through the surface of the mixture for 30 min. The mixture was warmed to ambient temperature and stirred for an additional 15 min. The volatiles were evaporated and to the residue was added water (50 mL) and sodium acetate trihydrate (9.55 g, 70.2 mmol). The solution was cooled on an ice bath and hydroxylamine-O-sulfonic acid (4.62 g, 40.9 mmol) was added. The mixture was stirred at ambient temperature for 1 h, extracted with ethylacetate (3×100 mL) and the combined extracts were washed with a sodium bicarbonate solution, brine and dried over molecular sieves. Evaporation to dryness gave a viscous liquid (4.93 g), which was chromatographed on silica eluting with 33% ethylacetate-hexane, to give a solid (2.47 g, 72%): mp 200°-202° C.

Workup

  1. customthe ice bath was removed
  2. waitthe stirring was continued for 30 min
  3. customAt this time a white precipitate formed
  4. temperatureThe mixture was cooled to -60° C.
  5. temperatureThe mixture was warmed to ambient temperature
  6. stirringstirred for an additional 15 min
  7. customThe volatiles were evaporated and to the residue
  8. temperatureThe solution was cooled on an ice bath
  9. stirringThe mixture was stirred at ambient temperature for 1 h
  10. extractionextracted with ethylacetate (3×100 mL)
  11. washthe combined extracts were washed with a sodium bicarbonate solution, brine
  12. customdried over molecular sieves
  13. customEvaporation to dryness

Sources & evidence

ORD record
ord-b4b992194aca49b79b5f712150a50132
Source dataset
uspto-grants-1992_10
Patent number
US05153192

Reaction notes

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