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

HRID 2307106Notes

Reaction equation

HRID 2307106 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-9e4d0aaca3ad4040b478a3054aa655b6
Source dataset
uspto-grants-2004_12
Patent number
US06828460B2

Reaction notes

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