Hydrochloric Acid → 4-(4-(2-(4-n-Pentylcyclohexyl)ethyl)-3-cyclohexenyl)cyclohexanone

HRID 2119283Notes

Reaction equation

HRID 2119283 reaction equation
[Mg].[CH2:2]([CH:7]1[CH2:12][CH2:11][CH:10]([CH2:13][CH2:14]Br)[CH2:9][CH2:8]1)[CH2:3][CH2:4][CH2:5][CH3:6].C1O[C:19]2([C:24](=O)[CH2:23][CH2:22][CH2:21][CH:20]2[CH:26]2[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]2)OC1.Cl.C1C[O:37]CC1>>[CH2:2]([CH:7]1[CH2:12][CH2:11][CH:10]([CH2:13][CH2:14][C:23]2[CH2:22][CH2:21][CH:20]([CH:26]3[CH2:31][CH2:30][C:29](=[O:37])[CH2:28][CH2:27]3)[CH2:19][CH:24]=2)[CH2:9][CH2:8]1)[CH2:3][CH2:4][CH2:5][CH3:6]

Participants

6

Reactant 5

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran2×HCID 5462224MagnesiumHCID 15114353trans-1-(Bromoethyl)-4-pentylcyclohexaneHCID 86759325Bicyclohexanedione monoethylene ketal

Product 1

HCID 234403814-(4-(2-(4-n-Pentylcyclohexyl)ethyl)-3-cyclohexenyl)cyclohexanone

Procedure

To the Grignard reagent which was prepared from 4.80 g (198 mmol) of dried magnesium and 50.0 g (191 mmol) of 2-(4-n-pentylcyclohexyl)bromoethane in 500 ml of THF, was added dropwise 200 ml of solution of 40.0 g (168 mmol) of bicyclohexanedione monoethylene ketal in THF at room temperature, and the mixture was stirred at the same temperature for 12 hours. The reaction solution was added to 500 ml of 0.5N hydrochloric acid, the product thus formed was extracted with ether, the extract was washed with saturated aqueous sodium bicarbonate solution and water in this turn, and then the solvent was distilled off. After the residue was purified by column chromatography on silica gel (eluent: heptane/ethyl acetate=3/1), the solvent was distilled off, the residue was refluxed in 200 ml of formic acid for 3 hours, 200 ml of water was added to the reaction solution, the product thus formed was extracted with toluene, the extract was washed with water, saturated aqueous sodium bicarbonate solution, and water in this turn, and then dried over magnesium sulfate. After the solvent was distilled off and the residue was purified by column chromatography (eluent: heptane/ethyl acetate=1/1), the solvent was distilled off, and the residue was recrystallized from ethanol to give 15.0 g of 4-(4-(2-(4-n-pentylcyclohexyl)-ethyl)-3-cyclohexenyl)-cyclohexanone. Yield of this compound based on bicyclohexanedione monoethylene ketal was 24.9%.

Workup

  1. customthe product thus formed
  2. extractionwas extracted with ether
  3. washthe extract was washed with saturated aqueous sodium bicarbonate solution and water in this turn
  4. distillationthe solvent was distilled off
  5. customAfter the residue was purified by column chromatography on silica gel (eluent: heptane/ethyl acetate=3/1)
  6. distillationthe solvent was distilled off
  7. temperaturethe residue was refluxed in 200 ml of formic acid for 3 hours
  8. addition200 ml of water was added to the reaction solution
  9. customthe product thus formed
  10. extractionwas extracted with toluene
  11. washthe extract was washed with water, saturated aqueous sodium bicarbonate solution, and water in this turn
  12. dry with materialdried over magnesium sulfate
  13. distillationAfter the solvent was distilled off
  14. customthe residue was purified by column chromatography (eluent: heptane/ethyl acetate=1/1)
  15. distillationthe solvent was distilled off
  16. customthe residue was recrystallized from ethanol

Sources & evidence

ORD record
ord-77ed222a4a9442dea201c8bbb3e5b23f
Source dataset
uspto-grants-2004_02
Patent number
US06685995B1

Reaction notes

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