Cyclohexanone → Ethyl cyclohexylideneacetate

HRID 1244451Notes

Reaction equation

HRID 1244451 reaction equation
C([Li])CCC.CN1CCCN(C)C1=[O:14].[C:15]1(=O)[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1.[CH2:22]1[CH2:26][O:25][CH2:24][CH2:23]1>Cl>[CH2:24]([O:25][C:26](=[O:14])[CH:22]=[C:15]1[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1)[CH3:23]

Participants

6

Reactant 4

HCID 7967CyclohexanoneHCID 8028Tetrahydrofuran2×HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 178418339Butyllithium

Product 1

HCID 73776Ethyl cyclohexylideneacetateYield 89%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Conditions

Temperature
-78 °C

Procedure

Triethylphosphonoacetate (5.0 g, 22.3 mmol) was dissolved in THF (25 mL) and cooled to −78° C. under a nitrogen blanket. n-Butyllithium (1.6 M in hexanes, 13.9 mL, 22.3 mmol) was added dropwise via syringe followed by the addition of 1,3-dimethyl-3,4,5,6-tetrahydro-2-(1H)-pyrimidinone (3 mL). The reaction was stirred at −78° C. for 15 minutes. A solution of cyclohexanone (1.1 g, 11.2 mmol) dissolved in THF (5 mL) was added. The mixture was allowed to warm to room temperature, and stirred for 18 hours. The reaction was diluted with 1N HCl and extracted with EtOAc, then washed with water, dried (Na2SO4), and concentrated in vacuo to provide 1.7 g (89%) of Intermediate 3 as an oil. 1H NMR (DMSO-d6) δ: 1.15 (t, J=7 Hz, 3H), 1.55 (br s, 6H), 2.2 (br s, 2H), 2.75 (br s, 2H), 4.05 (q, J=7 Hz, 2H), 5.6 (s, 1H).

Workup

  1. additionwas added
  2. temperatureto warm to room temperature
  3. stirringstirred for 18 hours
  4. extractionextracted with EtOAc
  5. washwashed with water
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b24d16abf2e94a979c84c1affae4c9b5
Source dataset
uspto-grants-2006_10
Patent number
US07122554B2

Reaction notes

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