Carbon Dioxide → (E)-4-(3-Chloro-4-cyclohexyl-phenyl)-3-pentene-2-one

HRID 1605662Notes

Reaction equation

HRID 1605662 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:14](=O)[CH3:15])[CH:5]=[CH:6][C:7]=1[CH:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1.C([O:19]/[C:20](/[CH3:27])=[CH:21]/C(OCC)=O)C.Cl.C(=O)=O>CN(C)C=O>[Cl:1][C:2]1[CH:3]=[C:4](/[C:14](/[CH3:15])=[CH:21]/[C:20](=[O:19])[CH3:27])[CH:5]=[CH:6][C:7]=1[CH:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 5354173Ethyl (2E)-3-ethoxy-2-butenoateHCID 109006461-(3-Chloro-4-cyclohexylphenyl)ethanone

Product 1

HCID 68133285(E)-4-(3-Chloro-4-cyclohexyl-phenyl)-3-pentene-2-one

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

87.6 Gm (0.781 mol) of potassium-tert.butylate were added all at once to a solution of 185.0 gm (0.781 mol) of 3'-chloro-4'-cyclohexyl-acetophenone and 123.0 gm (0.777 mol) of ethyl (E)-3-ethoxy-crotonate in 1.1 liters of anhydrous dimethyl formamide, whereby the temperature rose spontaneously from +20° to +38°C and the mixture turned deep red. The mixture was stirred for another hour with the temperature being maintained at 32°-35°C, and then 200 ml of concentrated hydrochloric acid added dropwise to the still warm mixture, and the resulting mixture was heated for 60 minutes at a temperature of 90°-100°C. After carbon dioxide evolution had ceased, the cooled mixture was stirred into 1 liter of ice water, and the aqueous mixture was exhaustively extracted with ether. The combined ether extracts were washed with water, dried over sodium sulfate and concentrated by evaporation. The residue was distilled in a vacuum (b.p. 175°-183°C at 0.1 mm Hg) and subsequently recrystallized twice from methanol, in the presence of activated charcoal. The colorless crystals, m.p. 56.5°-57.5°C were obtained with a yield of 132 gm (61% of theory).

Workup

  1. customrose spontaneously from +20° to +38°C
  2. temperaturebeing maintained at 32°-35°C
  3. temperaturethe resulting mixture was heated for 60 minutes at a temperature of 90°-100°C
  4. extractionthe aqueous mixture was exhaustively extracted with ether
  5. washThe combined ether extracts were washed with water
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated by evaporation
  8. distillationThe residue was distilled in a vacuum (b.p. 175°-183°C at 0.1 mm Hg)
  9. customsubsequently recrystallized twice from methanol, in the presence of activated charcoal
  10. customThe colorless crystals, m.p. 56.5°-57.5°C were obtained with a yield of 132 gm (61% of theory)

Sources & evidence

ORD record
ord-2b6409e3604a463ca5de409ad9f40d10
Source dataset
uspto-grants-1976_04
Patent number
US03950427

Reaction notes

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