(+/-)-3-[2,4-Bis(methoxymethoxy)phenyl]cyclohexanone → (+/-)-2,4-Bis(methoxymethoxy)-1-(3-methylenecyclohexyl)benzene

HRID 585642Notes

Reaction equation

HRID 585642 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][O:8][CH2:9][O:10][C:11]1[CH:16]=[C:15]([O:17][CH2:18][O:19][CH3:20])[CH:14]=[CH:13][C:12]=1[CH:21]1[CH2:26][CH2:25][CH2:24][C:23](=O)[CH2:22]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH3:7][O:8][CH2:9][O:10][C:11]1[CH:16]=[C:15]([O:17][CH2:18][O:19][CH3:20])[CH:14]=[CH:13][C:12]=1[CH:21]1[CH2:26][CH2:25][CH2:24][C:23](=[CH2:1])[CH2:22]1

Participants

5

Reactant 2

HCID 22337753(+/-)-3-[2,4-Bis(methoxymethoxy)phenyl]cyclohexanoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 22337755(+/-)-2,4-Bis(methoxymethoxy)-1-(3-methylenecyclohexyl)benzeneYield 81%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Potassium tert-butoxide (50 mg) was added to a suspension of methyltriphenylphosphonium bromide in tetrahydrofuran (4 ml) at 0° C. After 0.5 hr, a solution of (±)-3-[2,4-bis(methoxymethoxy)phenyl]cyclohexanone (100 mg) in tetrahydrofuran (1 ml) was added, and the mixture was allowed to warm to ambient temperature. After 16 hr, the reaction mixture was partitioned between ammonium chloride (30 ml of a saturated aqueous solution) and ethyl acetate. The aqueous layer was extracted with further ethyl acetate (2×30 ml), and the combined organic extracts were washed with brine (30 ml), dried over magnesium sulfate, and evaporated in vacuo. The crude residue was purified by flash column chromatography (SiO2, ethyl acetate/petrol, 4:1 v/v) to furnish the title compound as pale yellow oil (80 mg, 81%). δH (CDCl3) 1.50 (2H, m), 1.90 (2H, m), 2.05 (1H, m), 2.16 (1H, m), 2.35 (1H, m), 2.44 (1H, m), 2.97 (1H, m), 3.44 (3H, s), 3.48 (3H, s), 4.64 (1H, s), 4.69 (1H, s), 5.13 (2H, s), 5.17 (2H, s), 6.68 (1H, m), 6.77 (1H, m), 7.12 (1H, d).

Workup

  1. waitAfter 16 hr
  2. customthe reaction mixture was partitioned between ammonium chloride (30 ml of a saturated aqueous solution) and ethyl acetate
  3. extractionThe aqueous layer was extracted with further ethyl acetate (2×30 ml)
  4. washthe combined organic extracts were washed with brine (30 ml)
  5. dry with materialdried over magnesium sulfate
  6. customevaporated in vacuo
  7. customThe crude residue was purified by flash column chromatography (SiO2, ethyl acetate/petrol, 4:1 v/v)

Sources & evidence

ORD record
ord-5e4c513370ad441f9c32870c21716bce
Source dataset
uspto-grants-2005_08
Patent number
US06933319B2

Reaction notes

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