Hydrochloric Acid → 3-Methyl-2-sulfanylphenol

HRID 2215261Notes

Reaction equation

HRID 2215261 reaction equation
N([O-])=O.[Na+].Cl.N[C:7]1[C:12]([OH:13])=[CH:11][CH:10]=[CH:9][C:8]=1[CH3:14].O(CC)C([S-])=[S:17].[K+].[OH-].[K+]>O.C(O)C>[OH:13][C:12]1[CH:11]=[CH:10][CH:9]=[C:8]([CH3:14])[C:7]=1[SH:17]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 2735045Potassium ethylxanthateHCID 30141382-Amino-m-cresolHCID 23668193Sodium Nitrite

Product 1

HCID 217194883-Methyl-2-sulfanylphenol

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

5.3 g (0.077 mol) of sodium nitrite in solution in 12 ml of water are added dropwise to a round-bottomed flask comprising 14 g of ice, 14 ml of 36% hydrochloric acid and 8.62 g (0.07 mol) of 2-amino-m-cresol. The mixture, kept at 0° C., is subsequently poured slowly into a solution of 15 g (0.093 mol) of potassium ethyl xanthate in 20 ml of water held at 40° C. The heating bath is removed and the mixture is stirred for 3 hours and then extracted with ethyl ether. The combined organic phases are washed with aqueous saline solution, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue is purified by fast chromatography on silica gel (eluent: cyclohexane/dichloromethane=65:35). The oil obtained is taken up in 20 ml of ethanol and the mixture is heated to 100° C. 20 ml of an ethanolic potassium hydroxide solution (7N) are then added dropwise. After 4 hours at 100° C., the mixture is cooled, concentrated under reduced pressure, acidified using hydrochloric acid (2N) and then extracted with ethyl ether. The combined organic phases are dried over magnesium sulfate, filtered and concentrated under reduced pressure to give a yellow oil which is not isolated but is used directly in the following stage.

Workup

  1. customkept at 0° C.
  2. customheld at 40° C
  3. customThe heating bath is removed
  4. extractionextracted with ethyl ether
  5. washThe combined organic phases are washed with aqueous saline solution
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue is purified by fast chromatography on silica gel (eluent: cyclohexane/dichloromethane=65:35)
  10. customThe oil obtained
  11. waitAfter 4 hours at 100° C.
  12. temperaturethe mixture is cooled
  13. concentrationconcentrated under reduced pressure
  14. extractionextracted with ethyl ether
  15. dry with materialThe combined organic phases are dried over magnesium sulfate
  16. filtrationfiltered
  17. concentrationconcentrated under reduced pressure
  18. customto give a yellow oil which
  19. customis not isolated

Sources & evidence

ORD record
ord-294d1a374b814b69a4a179b62c61d63f
Source dataset
uspto-grants-2006_09
Patent number
US07109234B2

Reaction notes

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