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

HRID 1735986ノート

反応式

HRID 1735986 の反応式
[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

参加物

10

反応物 5

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 22902024HCID 22902024、化合物HCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

生成物 1

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

試薬・触媒・溶媒 4

HCID 8058Hexane触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-987f0326a8544d36a1cc6fd9e8d729d2
出典データセット
uspto-grants-1996_07
特許番号
US05538966

反応ノート

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