Dimethyl Sulfate → HCID 22665846, compound

HRID 619779Notes

Reaction equation

HRID 619779 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8]([S:12]([OH:15])(=[O:14])=[O:13])=[CH:9]2)=[CH:4][CH:3]=1.[Na].[OH-].[Na+].S(OC)(O[CH3:23])(=O)=O>O.C(O)C>[CH3:23][O:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8]([S:12]([OH:15])(=[O:13])=[O:14])=[CH:9]2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 70897-Hydroxy-2-naphthalenesulfonic acidHCID 14798Sodium HydroxideHCID 5360545Sodium

Product 1

HCID 22665846HCID 22665846, compound

Reagents, catalysts & solvents 1

HCID 19096565Water ethanolSolvent

Procedure

To a suspension of 7-hydroxynaphthalene-2-sulfonic acid, sodium salt (15 g, 60.9 mmol) in 150 mL of 2:1 H2O/ethanol 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 eventually 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 100 mL of absolute EtOH as a slurry for 2 hours. The precipitate is filtered and dried. The solid is heated at reflux in 100 mL of 95% EtOH for 2 hours, 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 20 mL of phosphorous oxychloride 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. additionis then added
  2. concentrationThe crude mixture is concentrated in vacuo
  3. stirringthe residue is stirred in 100 mL of absolute EtOH as a slurry for 2 hours
  4. filtrationThe precipitate is filtered
  5. customdried
  6. temperatureThe solid is heated
  7. temperatureat reflux in 100 mL of 95% EtOH for 2 hours
  8. filtrationfiltered
  9. customdried

Sources & evidence

ORD record
ord-5cfbdde9b74342fa8a59ee45df976f72
Source dataset
uspto-grants-1999_09
Patent number
US05958918

Reaction notes

Loading…