Dimethyl Sulfate → HCID 12763272, compound

HRID 68232Notes

Reaction equation

HRID 68232 reaction equation
[C:1]1([SH:8])[CH:6]=[CH:5][CH:4]=[C:3]([SH:7])[CH:2]=1.[CH3:9]C1CCCO1.COS(OC)(=O)=O.[OH-].[Na+]>C(OC)(C)(C)C>[CH3:9][S:7][C:3]1[CH:2]=[C:1]([SH:8])[CH:6]=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 73012-Methyltetrahydrofuran3×HCID 14798Sodium HydroxideHCID 5220621,3-Benzenedithiol

Product 1

HCID 12763272HCID 12763272, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
50 °C

Procedure

A solution of benzene-1,3-dithiol (50 g, 0.351 mmol) in 2-methyltetrahydrofuran (375 mL, 0.351 mmol) was treated with dimethylsulfate (33.3 mL, 0.351 mol) followed by 2-methyltetrahydrofuran (25 mL, used as line wash). The resulting solution was cooled to between 0° C. and 5° C. and sodium hydroxide (2M aqueous solution, 210.6 mL) was added drop wise maintaining the temperature of the reaction mixture below 15° C. followed by 2-methyltetrahydrofuran (25 mL, used as line wash) and heated under nitrogen to 50° C. for 4 hours. After cooling to ambient temperature the resulting solution was treated with tert-butylmethylether (500 mL) and the phases were separated. The organic phase was extracted with sodium hydroxide (2 M aqueous solution, 250 mL) and the combined aqueous phases were cooled to 10° C. and hydrochloric acid (6M aqueous solution, 500 mL) was added whilst maintaining the temperature of the mixture below 25° C. The resulting solution was extracted with tert-butylmethylether (2-fold 250 mL) and the combined organic phases were washed with water (500 mL) and concentrated in vacuo to give the title compound as a yellow oil, 78% yield, 42.9 g.

Workup

  1. temperatureThe resulting solution was cooled to between 0° C. and 5° C.
  2. temperaturewise maintaining the temperature of the reaction mixture below 15° C.
  3. temperatureAfter cooling to ambient temperature the resulting solution
  4. customthe phases were separated
  5. extractionThe organic phase was extracted with sodium hydroxide (2 M aqueous solution, 250 mL)
  6. temperaturethe combined aqueous phases were cooled to 10° C.
  7. additionhydrochloric acid (6M aqueous solution, 500 mL) was added
  8. temperaturewhilst maintaining the temperature of the mixture below 25° C
  9. extractionThe resulting solution was extracted with tert-butylmethylether (2-fold 250 mL)
  10. washthe combined organic phases were washed with water (500 mL)
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-62a5d83b7c594413a7da477ba5532a08
Source dataset
uspto-grants-2014_09
Patent number
US08822439B2

Reaction notes

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