Sulfur Dioxide → HCID 19374697, compound

HRID 128573Notes

Reaction equation

HRID 128573 reaction equation
[S:1]1(=[O:11])(=[O:10])[C:6]2[S:7][CH:8]=[CH:9][C:5]=2[CH:4]=[N:3][NH:2]1.C([Li])CCC.[S:17](=[O:19])=[O:18].O.O.O.C([O-])(=O)C.[Na+].[NH2:28]OS(O)(=O)=O>C1COCC1.O>[S:1]1(=[O:11])(=[O:10])[C:6]2[S:7][C:8]([S:17]([NH2:28])(=[O:19])=[O:18])=[CH:9][C:5]=2[CH:4]=[N:3][NH:2]1

Participants

8

Reactant 5

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 19374693HCID 19374693, compoundHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Product 1

HCID 19374697HCID 19374697, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

The product from step B (0.1 g, 5.3 mmol) was dissolved in dry THF (4 mL) and cooled to -78° C. under nitrogen. n-Butyllithium (0.7 mL of a 2.5 M solution in hexanes, 1.75 mmol) was added dropwise, the mixture stirred for 1h at -78° C. A stream of sulfur dioxide gas was passed through the surface of the mixture for 15 min. and then the mixture was allowed to warm to room temperature. Evaporation of the reaction mixture provided a residue which was dissolved in water (5 mL) to which was added sodium acetate trihydrate (0.21 g, 1.39 mmol); this solution was cooled to 0° C. and hydroxylamine-O-sulfonic acid (0.18 g, 1.39 mmol) was added followed by stirring for 18 h. The reaction mixture was extracted with ethyl acetate (2×5 mL). The combined extracts were dried over MgSO4 and concentrated to a crude oil which was purified by flash column chromatography (silica, hexane-ethyl acetate gradient) to give a white solid. (0.021 g, 15%). decomposition:t>183° C. Cl-MS m/e 268 (m+H)+. 1HNMR (DMSO-d6): δ:7.90 (1H, 1s, CH); 8.22 (2H, S, NH2 exchangeable); 8.34 (1H, 1s, CH=N).

Workup

  1. temperatureto warm to room temperature
  2. customEvaporation of the reaction mixture
  3. customprovided a residue which
  4. temperaturethis solution was cooled to 0° C.
  5. extractionThe reaction mixture was extracted with ethyl acetate (2×5 mL)
  6. dry with materialThe combined extracts were dried over MgSO4
  7. concentrationconcentrated to a crude oil which
  8. customwas purified by flash column chromatography (silica, hexane-ethyl acetate gradient)
  9. customto give a white solid
  10. customt>183° C

Sources & evidence

ORD record
ord-5c3fba516fbe4169b1de8d131e54ffd5
Source dataset
uspto-grants-1995_11
Patent number
US05464831

Reaction notes

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