Water → {4-[2,4-Bis(methoxymethoxy)phenyl]cyclohexylidene}acetonitrile

HRID 585668Notes

Reaction equation

HRID 585668 reaction equation
[H-].[Na+].[C:3]([CH2:5]P(=O)(OCC)OCC)#[N:4].[CH3:14][O:15][CH2:16][O:17][C:18]1[CH:23]=[C:22]([O:24][CH2:25][O:26][CH3:27])[CH:21]=[CH:20][C:19]=1[CH:28]1[CH2:33][CH2:32][C:31](=O)[CH2:30][CH2:29]1.O>COCCOC.C(OCC)C>[CH3:14][O:15][CH2:16][O:17][C:18]1[CH:23]=[C:22]([O:24][CH2:25][O:26][CH3:27])[CH:21]=[CH:20][C:19]=1[CH:28]1[CH2:33][CH2:32][C:31](=[CH:5][C:3]#[N:4])[CH2:30][CH2:29]1

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 121351704-[2,4-Bis(methoxymethoxy)phenyl]cyclohexanone

Product 1

HCID 22337767{4-[2,4-Bis(methoxymethoxy)phenyl]cyclohexylidene}acetonitrileYield 66%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a round bottomed flask equipped with magnetic stirrer was added sodium hydride (40 mg, 0.95 mmol, 60% dispersion in mineral oil). After washing the sodium hydride with petroleum ether (2×20 ml), the excess solvent was removed under reduced pressure. 1,2-Dimethoxyethane (10 ml) was added and the stirred suspension cooled to 0° C. Diethyl cyanomethylphosphonate (102 μl, 0.95 mmol) was added dropwise. The reaction mixture was allowed to warm slowly to room temperature over 2 hr. 4-[(2,4-Bis(methoxymethoxy)phenyl)]cyclohexanone (200 mg, 0.68 mmol) was then added as a solution in 1,2-dimethoxyethane (10 ml) and the reaction mixture stirred for 17 hr at room temperature. The reaction mixture was poured into a separating funnel containing water (50 ml) and diethyl ether (50 ml). The layers were separated and the aqueous phase extracted with diethyl ether (2×20 ml). The combined organic layers were washed with brine (20 ml), dried over magnesium sulfate, filtered and concentrated in vacuo, to give an oil. Purification via flash column chromatography (SiO2, ethyl acetate/petroleum ether, 1:2, v/v) afforded the title compound (141 mg, 66%) as a pale yellow oil. δH(CD3OD) 1.57-1.70 (2H, m), 2.02-2.25 (2H, m), 2.34-2.49 (2H, m), 2.60 (1H, m), 3.03 (1H, m), 3.24 (1H, m), 3.47 (3H, s), 3.52 (3H, s), 5.17 (2H, s), 5.23(2H, s), 5.33 (1H, s), 6.66 and 6.69 (1H, d), 6.83 (1H, d), 7.09 (1H, d

Workup

  1. customTo a round bottomed flask equipped with magnetic stirrer
  2. washAfter washing the sodium hydride with petroleum ether (2×20 ml)
  3. customthe excess solvent was removed under reduced pressure
  4. addition1,2-Dimethoxyethane (10 ml) was added
  5. temperatureto warm slowly to room temperature over 2 hr
  6. additionThe reaction mixture was poured into a separating funnel
  7. customThe layers were separated
  8. extractionthe aqueous phase extracted with diethyl ether (2×20 ml)
  9. washThe combined organic layers were washed with brine (20 ml)
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customto give an oil
  14. customPurification via flash column chromatography (SiO2, ethyl acetate/petroleum ether, 1:2

Sources & evidence

ORD record
ord-fa870f44e8254c1bba9467b0f728fb73
Source dataset
uspto-grants-2005_08
Patent number
US06933319B2

Reaction notes

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