Ethanethiol → 2-Ethylthio-4-t-butylphenol

HRID 745697Notes

Reaction equation

HRID 745697 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:12]([S:14]SCC)[CH3:13].C(S)C>C(O)CC.CCCO.CCCO.CCCO.CCCO.[Zr].[Zr]>[CH2:12]([S:14][C:9]1[CH:10]=[C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])[CH:6]=[CH:7][C:8]=1[OH:11])[CH3:13]

Participants

7

Reactant 3

HCID 6343EthanethiolHCID 73934-tert-Butylphenol2×HCID 8077Diethyl disulfide

Product 1

HCID 123826082-Ethylthio-4-t-butylphenolYield 49%

Reagents, catalysts & solvents 3

HCID 23995ZirconiumCatalystHCID 3539967Zirconium n-propoxideCatalystHCID 10311-PropanolSolvent2×

Conditions

Temperature
194 °C

Procedure

To 4-t-Butylphenol (10.0 g, 0.067 moles) was added 2.8 g zirconium n-propoxide in n-propanol consisting of 21.6% zirconium (0.007 mole) and 10.8% free propanol. The mixture was distilled at atmospheric pressure removing 1.8 g of n-propanol. To the mixture was added ethyl disulfide (8.2 g, 0.067 moles). The mixture was heated under nitrogen while ethyl mercaptan was removed continuously by distillation. Heating under nitrogen was continued for a total of 142 hours during which temperature slowly increased to 194° C. The mixture was cooled, hydrolyzed by addition of water, and made acid with concentrated HCl. The mixture was extracted with ether. The ether extracts were dried over magnesium sulfate, filtered, and concentrated on a rotary flash evaporator. GC analysis of the concentrate indicated only two major components, 2.5 g of 4-t-butylphenol and 6.8 g of 2-ethylthio-4-t-butylphenol (49% yield).

Workup

  1. distillationThe mixture was distilled at atmospheric pressure
  2. customremoving 1.8 g of n-propanol
  3. customwas removed continuously by distillation
  4. temperatureHeating under nitrogen
  5. customwas continued for a total of 142 hours during which temperature
  6. temperatureThe mixture was cooled
  7. additionhydrolyzed by addition of water
  8. extractionThe mixture was extracted with ether
  9. dry with materialThe ether extracts were dried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated on a rotary flash evaporator

Sources & evidence

ORD record
ord-f7126cb618444f4d92be9311afa33c48
Source dataset
uspto-grants-1986_07
Patent number
US04599451

Reaction notes

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