Water → Ethyl 4-methylidenecyclohexane-1-carboxylate

HRID 2201663Notes

Reaction equation

HRID 2201663 reaction equation
[Br-].C1(C([PH3+])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:22][C:23]([CH3:26])([O-])[CH3:24].[K+].O=C1C[CH2:33][CH:32]([C:35]([O:37][CH2:38][CH3:39])=[O:36])[CH2:31]C1.O>C1COCC1>[CH2:22]=[C:23]1[CH2:26][CH2:33][CH:32]([C:35]([O:37][CH2:38][CH3:39])=[O:36])[CH2:31][CH2:24]1

Participants

6

Reactant 4

HCID 962WaterHCID 317638Ethyl 4-oxocyclohexanecarboxylate2×HCID 21951224Triphenylmethyl phosphonium bromideHCID 23665647Potassium tert-butoxide

Product 1

HCID 15151435Ethyl 4-methylidenecyclohexane-1-carboxylateYield 95.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Triphenylmethylphosphonium bromide (53.7 g, 0.15 mol) was dissolved in 500 mL of THF, and potassium tert-butoxide (16.8 g, 0.15 mol) was added at −20° C. Reacted for 0.5 h after the temperature was raised to 0° C. Subsequently, ethyl 4-oxo-cyclohexylcarboxylate (Compound 8-1) (17 g, 0.1 mol) was dissolved in 100 mL of THF and added dropwise to the flask under nitrogen, reacted at room temperature for 3 hours, then a small amount of water was added to dissolve the solid, and rotary evaporated to remove THF, extracted with anhydrous diethyl ether, dried, and concentrated, the concentrate was dissolved in n-hexane, and filtered by silica gel, then concentrated to give Compound 8-2 as a colorless liquid (16.1 g, 95.7% yield).

Workup

  1. customReacted for 0.5 h after the temperature
  2. additionadded dropwise to the flask under nitrogen
  3. customreacted at room temperature for 3 hours
  4. dissolutionto dissolve the solid
  5. customrotary evaporated
  6. customto remove THF
  7. extractionextracted with anhydrous diethyl ether
  8. customdried
  9. concentrationconcentrated
  10. dissolutionthe concentrate was dissolved in n-hexane
  11. filtrationfiltered by silica gel
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-8f93d399ebd24ff3b54a21949b5c66b1
Source dataset
uspto-grants-2016_06
Patent number
US09365499B2

Reaction notes

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