Dimethyl Sulfate → HCID 4337105, compound

HRID 619784Notes

Reaction equation

HRID 619784 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([S:12]([OH:15])(=[O:14])=[O:13])[CH:6]=[CH:5]2.[Na].[OH-].[Na+].S(OC)(O[CH3:23])(=O)=O>O.C(O)C>[CH3:23][O:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([S:12]([OH:15])(=[O:13])=[O:14])[CH:6]=[CH:5]2

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 71176-Hydroxynaphthalene-2-sulfonic acidHCID 14798Sodium HydroxideHCID 5360545Sodium

Product 1

HCID 4337105HCID 4337105, compound

Reagents, catalysts & solvents 1

HCID 19096565Water ethanolSolvent

Procedure

To a suspension of 6-hydroxynaphthalene-2-sulfonic acid, sodium salt (5 g, 20.3 mmol) in 40 mL of 2:1 H2O/ethanol is added solid NaOH (0.89 g, 22.3 mmol) at room temperature. The resulting black mixture is stirred until a homogenous solution forms, and dimethyl sulfate (2.11 mL, 22.3 mmol) is then added. The mixture is stirred over a period of 16 hours as a precipitate eventually forms. The crude mixture is concentrated in vacuo and the residue is stirred in 70 mL of absolute EtOH as a slurry. The precipitate is filtered and dried. The solid is heated at reflux in 100 mL of 95% EtOH for 2.5 hours allowed to cool to room temperature, filtered and dried to give 3.31 g of crude 6-methoxynaphthalene-2-sulfonic acid, sodium salt. A mixture of the sulfonic acid, sodium salt (3.31 g, 12.7 mmol) in 5.3 mL of phosphorous oxychloride and phosphorous pentachloride (3.44 g, 16.5 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 allowed to stir at room temperature overnight, then is added slowly to a mixture of ice/ice water. The mixture is diluted with water and extracted with CHCl3. The combined organic layers are washed successively with water and saturated NaHCO3 solution. The organic phase is dried over anhydrous MgSO4, filtered and concentrated to give 4 g of a crude product. The crude product is purified by column chromatography in a gradient of 10% EtOAc/hexanes to 20% EtOAc/hexanes to afford the title compound (1.51 g, 5.88 mmol) as a crystalline solid.

Workup

  1. additionis then added
  2. concentrationThe crude mixture is concentrated in vacuo
  3. stirringthe residue is stirred in 70 mL of absolute EtOH as a slurry
  4. filtrationThe precipitate is filtered
  5. customdried
  6. temperatureThe solid is heated
  7. temperatureat reflux in 100 mL of 95% EtOH for 2.5 hours
  8. filtrationfiltered
  9. customdried

Sources & evidence

ORD record
ord-1a3a4730c8c94b588b1fac661500c429
Source dataset
uspto-grants-1999_09
Patent number
US05958918

Reaction notes

Loading…