Diethyl Ether → 2-Allyl-6-[(butylthio)methylene]-2-ethylcyclohexanone

HRID 65615Notes

Reaction equation

HRID 65615 reaction equation
[CH3:1][C:2](C)([O-])C.[K+].[CH2:7]([S:11][CH:12]=[C:13]1[CH2:18][CH2:17][CH2:16][CH:15]([CH2:19][CH3:20])[C:14]1=[O:21])[CH2:8][CH2:9][CH3:10].[CH2:22](Br)C=C.CCOCC>CCCCCC>[CH2:19]([C:15]1([CH2:1][CH3:2])[CH2:16][CH2:17][CH2:18][C:13](=[CH:12][S:11][CH2:7][CH2:8][CH2:9][CH3:10])[C:14]1=[O:21])[CH:20]=[CH2:22]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 7841Allyl bromideHCID 23665647Potassium tert-butoxideHCID 537663082-[(Butylthio)methylene]-6-ethylcyclohexanone

Product 1

HCID 545033622-Allyl-6-[(butylthio)methylene]-2-ethylcyclohexanone

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

To a well stirred solution of potassium tert-butoxide (17.95 g, 0.16 mole) in dry redistilled tert-butanol (160 ml) under nitrogen, 2-[(butylthio)methylene]6-ethylcylcohexanone (9.05 g, 0.04 mole), described in Example 3, is added slowly. The mixture is stirred at room temperature for 5 minutes and then chilled in an ice bath. Allyl bromide (21.8 g, 0.18 mole) is added rapidly to the chilled mixture. The mixture is then stirred at room temperature for 48 hr. Most of the solvent is then removed under reduced pressure and water (about 150 ml) is added. The aqueous solution is extracted with ether (3 ×). The combined ether extracts are washed with brine, dried (MgSO4) and concentrated to yield an oil. The oil is subjected to chromotography on silica gel (320 g) using 4% ether in hexane as eluant. Concentration of the eluate gives 2-allyl-6-[(butylthio)methylene]-2-ethylcyclohexanone, nmr(CDCl3) δ 0.85 (t, J=7, 3H), 2.85 (t, J=7, 2H), 4.80 - 6.0 (m, 3H), 7.5 (t, J=2, 1H).

Workup

  1. distillationredistilled tert-butanol (160 ml) under nitrogen
  2. additionis added slowly
  3. temperaturechilled in an ice bath
  4. stirringThe mixture is then stirred at room temperature for 48 hr
  5. customMost of the solvent is then removed under reduced pressure and water (about 150 ml)
  6. additionis added
  7. extractionThe aqueous solution is extracted with ether (3 ×)
  8. washThe combined ether extracts are washed with brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. customto yield an oil

Sources & evidence

ORD record
ord-cc9b0ea6a2494f1084cf3ac49292cdbb
Source dataset
uspto-grants-1978_12
Patent number
US04128560

Reaction notes

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