Phosphorus pentachloride → 7-methoxynaphthalene-2-sulfonyl Chloride

HRID 651595Notes

Reaction equation

HRID 651595 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH:7]=[CH:8][C:9]([S:13]([OH:16])(=O)=[O:14])=[CH:10]2)=[CH:5][CH:4]=1.[Na].P(Cl)(Cl)(Cl)(Cl)[Cl:19]>P(Cl)(Cl)(Cl)=O.O>[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH:7]=[CH:8][C:9]([S:13]([Cl:19])(=[O:16])=[O:14])=[CH:10]2)=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 24819Phosphorus pentachlorideHCID 5360545SodiumHCID 22665846HCID 22665846, compound

Product 1

HCID 105152667-methoxynaphthalene-2-sulfonyl Chloride

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 24813Phosphorus oxychlorideSolvent

Conditions

Temperature
60 °C

Procedure

To a suspension of 7-hydroxynaphthalene-2-sulfonic acid, sodium salt (15 g, 60.9 mmol) in H2O/ethanol (150 mL, 2:1) is added solid NaOH (2.68 g, 67 mmol) at room temperature. The mixture is stirred until a homogenous solution forms and dimethyl sulfate (6.34 mL, 67 mmol) is then added. A precipitate slowly forms and the mixture is stirred over a period of 16 hours. The crude mixture is concentrated in vacuo and the residue is stirred in absolute EtOH (100 mL) as a slurry for 2 hours. The precipitate is filtered and dried. The solid is heated at reflux in 95% EtOH (100 mL) for 2 h, allowed to cool to room temperature, filtered and dried to give 12.6 g of crude 7-methoxynaphthalene-2-sulfonic acid, sodium salt. A mixture of the sulfonic acid, sodium salt (12.6 g, 48.6 mmol) in phosphorous oxychloride (20 mL) and phosphorous pentachloride (13.2 g, 63.2 mmol) is heated slowly to 60° C. until a homogenous solution forms and then is heated at 120° C. for 4 hours. The resulting mixture is cooled in an ice bath and a mixture of ice/ice water is added slowly with stirring. The mixture is diluted with water and extracted with CHCl3 (2×100 mL). The combined organic layers are washed successively with water, saturated NaHCO3 solution and saturated NaCl. The organic phase is dried over anhydrous MgSO4, filtered and concentrated to give 10 g of a crude oil. The crude product is purified by column chromatography in a gradient of 5% EtOAc/hexanes to 30% EtOAc/hexanes to afford the title compound (3.8 g, 14.8 mmol) as a white crystalline solid.

Workup

  1. temperatureis heated at 120° C. for 4 hours
  2. temperatureThe resulting mixture is cooled in an ice bath
  3. additionis added slowly
  4. extractionextracted with CHCl3 (2×100 mL)
  5. washThe combined organic layers are washed successively with water, saturated NaHCO3 solution and saturated NaCl
  6. dry with materialThe organic phase is dried over anhydrous MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give 10 g of a crude oil
  10. customThe crude product is purified by column chromatography in a gradient of 5% EtOAc/hexanes to 30% EtOAc/hexanes

Sources & evidence

ORD record
ord-89e6c607d9f04fe790c16e701fd3bfc8
Source dataset
uspto-grants-2001_08
Patent number
US06281227B1

Reaction notes

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