Potassium Hydroxide → 3-(2-Chlorophenylthio)-4-ketocyclohexane acetic acid ethyl ester

HRID 1856517Notes

Reaction equation

HRID 1856517 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[SH:8].[OH-].[K+].[CH2:11]([O:13][C:14](=[O:24])[CH2:15][CH:16]1[CH2:21][CH2:20][C:19](=[O:22])[CH:18](Br)[CH2:17]1)[CH3:12]>C(O)C>[CH2:11]([O:13][C:14](=[O:24])[CH2:15][CH:16]1[CH2:21][CH2:20][C:19](=[O:22])[CH:18]([S:8][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[Cl:1])[CH2:17]1)[CH3:12]

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 80599o-ChlorothiophenolHCID 130650933-Bromo-4-ketocyclohexaneacetic acid ethyl ester

Product 1

HCID 130651293-(2-Chlorophenylthio)-4-ketocyclohexane acetic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

28 G. of 2-chlorothiophenol and a solution of 10.8 g. of 85% potassium hydroxide in 300 ml. of ethanol were each placed in a 3 liter three-necked flask, provided with a condenser, nitrogen inlet, dropping funnel and stirrer. The solution was brought to reflux and a solution of 50.6 g. of 3-bromo-4-ketocyclohexaneacetic acid ethyl ester in 500 ml. of ethanol was added over a period of one hour to the refluxing solution. After the addition, the solution was stirred at reflux for one hour, cooled to room temperature, and filtered to remove the potassium bromide. After removal of the ethanol in vacuo (steam bath, rotovapor), 300 ml. of water was added to the residue, the product was extracted three times with 200 ml. of ether and the ether extract dried over anhydrous magnesium sulfate. After removal of ether from a steam bath at atmospheric pressure, the residue was distilled in vacuo. A forerun was collected at 100°-190° (1 mm), while a main fraction was collected at 190° -222° (1 mm). The yield of 3-(2-chlorophenylthio)-4-ketocyclohexaneacetic acid ethyl ester from the main fraction was 33.9 g., b.p. 205-215/0.7 mm.

Workup

  1. customeach placed in a 3 liter three-necked flask
  2. customprovided with a condenser, nitrogen inlet
  3. temperatureto reflux
  4. additionAfter the addition
  5. temperatureat reflux for one hour
  6. filtrationfiltered
  7. customto remove the potassium bromide
  8. customAfter removal of the ethanol in vacuo (steam bath, rotovapor), 300 ml
  9. additionof water was added to the residue
  10. extractionthe product was extracted three times with 200 ml
  11. extractionof ether and the ether extract
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customAfter removal of ether from a steam bath at atmospheric pressure
  14. distillationthe residue was distilled in vacuo
  15. customA forerun was collected at 100°-190° (1 mm)
  16. customwhile a main fraction was collected at 190° -222° (1 mm)

Sources & evidence

ORD record
ord-31b80c69b4de4cbc908420fbc112c9fa
Source dataset
uspto-grants-1980_08
Patent number
US04219657

Reaction notes

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