tert-Butanol → 2-Allyl-6-[(butylthio)methylene]-2-ethylcyclohexanone

HRID 1438915Notes

Reaction equation

HRID 1438915 reaction equation
[CH3:1][C:2](C)([O-])C.[K+].[C:7](O)(C)(C)C.[CH2:12]([S:16][CH:17]=[C:18]1[CH2:23][CH2:22][CH2:21][CH:20]([CH2:24][CH3:25])[C:19]1=[O:26])[CH2:13][CH2:14][CH3:15].C(Br)C=C>CCCCCC.CCOCC>[CH2:24]([C:20]1([CH2:1][CH3:2])[CH2:21][CH2:22][CH2:23][C:18](=[CH:17][S:16][CH2:12][CH2:13][CH2:14][CH3:15])[C:19]1=[O:26])[CH:25]=[CH2:7]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 7841Allyl bromideHCID 23665647Potassium tert-butoxideHCID 537663082-[(Butylthio)methylene]-6-ethylcyclohexanone

Product 1

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

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a well stirred solution of potassium tert-butoxide (17.95 g, 0.16 mole) in dry redistilled tert-butanol (160 ml) 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 x). The combined ether extracts are washed with brine, dried (MgSO4) and concentrated to yield 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. additionis added slowly
  2. temperaturechilled in an ice bath
  3. stirringThe mixture is then stirred at room temperature for 48 hr
  4. customMost of the solvent is then removed under reduced pressure and water (about 150 ml)
  5. additionis added
  6. extractionThe aqueous solution is extracted with ether (3 x)
  7. washThe combined ether extracts are washed with brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customto yield oil

Sources & evidence

ORD record
ord-ad607d2a537d4cc48bda80b8e410ab35
Source dataset
uspto-grants-1977_11
Patent number
US04057559

Reaction notes

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