1,4-Cyclohexanedione → Methyl 2-(4-oxocyclohexylidene)propanoate

HRID 522237Notes

Reaction equation

HRID 522237 reaction equation
C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)=[C:8]([CH3:13])[C:9]([O:11][CH3:12])=[O:10])C=CC=CC=1.[C:26]1(=[O:33])[CH2:31][CH2:30][C:29](=O)[CH2:28][CH2:27]1>C1(C)C=CC=CC=1>[O:33]=[C:26]1[CH2:27][CH2:28][C:29](=[C:8]([CH3:13])[C:9]([O:11][CH3:12])=[O:10])[CH2:30][CH2:31]1

Participants

4

Reactant 2

HCID 125111,4-CyclohexanedioneHCID 10569721Methyl 2-(triphenyl-lambda~5~-phosphanylidene)propanoate

Product 1

HCID 118274233Methyl 2-(4-oxocyclohexylidene)propanoate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of methyl 2-(triphenylphosphoranylidene)propanoate (2.5 g, 7.18 mmol) and cyclohexane-1,4-dione (1.609 g, 14.35 mmol) in toluene (25 mL) was stirred at 100° C. overnight and then concentrated in vacuo. The residue was triturated with a mixture of hexanes (100 mL) and ethyl acetate (100 mL), and filtered. The filtrate was concentrated in vacuo and the residue was purified by flash chromatography on Analogix IntelliFlash280 eluting with 0 to 50% ethyl acetate/hexanes to provide the title compound. 1H NMR (400 MHz, DMSO-d6) δ 1.85 (p, J=1.5 Hz, 3H), 2.27-2.35 (m, 2H), 2.41 (dd, J=8.0, 5.8 Hz, 2H), 2.55-2.65 (m, 2H), 2.81-2.90 (m, 2H), 3.66 (s, 3H).

Workup

  1. concentrationconcentrated in vacuo
  2. customThe residue was triturated with a mixture of hexanes (100 mL) and ethyl acetate (100 mL)
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated in vacuo
  5. customthe residue was purified by flash chromatography on Analogix IntelliFlash280
  6. washeluting with 0 to 50% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-878ce4b42598475db3bca782a7a9cd74
Source dataset
uspto-grants-2016_05
Patent number
US09328112B2

Reaction notes

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