Dimethyl Sulfoxide → 4-Tert-butyl-2-(methylsulfanyl)phenol

HRID 236919Notes

Reaction equation

HRID 236919 reaction equation
[CH3:1][C:2]([C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[CH:7][CH:6]=1)([CH3:4])[CH3:3].P(Cl)(Cl)(Cl)=O.[CH3:17][S:18](C)=O>Cl(O)(=O)(=O)=O>[CH3:17][S:18][C:9]1[CH:10]=[C:5]([C:2]([CH3:1])([CH3:3])[CH3:4])[CH:6]=[CH:7][C:8]=1[OH:11]

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 73934-tert-ButylphenolHCID 24813Phosphorus oxychloride

Product 1

HCID 123826074-Tert-butyl-2-(methylsulfanyl)phenol

Reagents, catalysts & solvents 1

HCID 24247Perchloric AcidSolvent

Conditions

Temperature
20 °C

Procedure

To a cold (0°-5° C.) suspension of 4-(1,1-dimethylethyl)phenol (7.5 g., 0.05 mole) and phosphorous oxychloride (8 ml.) in 70% perchloric acid (10 ml.) is added dimethylsulfoxide (3.9 g., 0.05 mole) dropwise with vigorous stirring. The resulting reaction mixture is stirred at 0°-5° C. for 1 hour and at 20° C. for 16 hours and then poured onto crushed ice whereupon a gum separates. Upon warming to 20° C. with vigorous stirring there is obtained a white solid which is collected, washed with cold water, air dried at 20° C. with aspiration and washed with ether. The white solid (10 g., m.p. 160° C.) is added to saturated aqueous potassium chloride (100 ml.) and the resulting mixture, heated at reflux for 4 hours. After standing at 20° C. for 12 hours, the reaction mixture is extracted with ether. The ethereal extract is washed with water and saturated brine, dried over sodium sulfate and filtered. Evaporation of the filtrate in vacuo leaves 2-methylthio-4-(1,1-dimethylethyl)phenol as an analytically pure, colorless oil (5.7 g., 58%).

Workup

  1. customThe resulting reaction mixture
  2. additionpoured
  3. customonto crushed ice whereupon a gum
  4. temperatureUpon warming to 20° C.
  5. stirringwith vigorous stirring there
  6. customis obtained a white solid which
  7. customis collected
  8. washwashed with cold water, air
  9. customdried at 20° C. with aspiration
  10. washwashed with ether
  11. additionThe white solid (10 g., m.p. 160° C.) is added to saturated aqueous potassium chloride (100 ml.)
  12. temperaturethe resulting mixture, heated
  13. temperatureat reflux for 4 hours
  14. waitAfter standing at 20° C. for 12 hours
  15. extractionthe reaction mixture is extracted with ether
  16. extractionThe ethereal extract
  17. washis washed with water and saturated brine
  18. dry with materialdried over sodium sulfate
  19. filtrationfiltered
  20. customEvaporation of the filtrate in vacuo

Sources & evidence

ORD record
ord-9b52e6e117dd4287bca34a2798c2e15d
Source dataset
uspto-grants-1979_06
Patent number
US04159279

Reaction notes

Loading…