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

HRID 1605656Notes

Reaction equation

HRID 1605656 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[C:6]([Cl:16])[CH:5]=1)(=O)[CH3:2].[CH2:17]([O:19]/C(/C)=C/C(OCC)=O)[CH3:18].Cl.[C:29](=O)=O>CN(C)C=O>[Cl:16][C:6]1[CH:5]=[C:4](/[C:1](/[CH3:29])=[CH:2]/[C:17](=[O:19])[CH3:18])[CH:9]=[CH:8][C:7]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 5354173Ethyl (2E)-3-ethoxy-2-butenoateHCID 127880424-Acetyl-2-chloro-biphenyl

Product 1

HCID 68133660(E)-4-(2-Chloro-4-biphenylyl)-3-pentene-2-one

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

208.0 Gm (1.85 mols) of potassium tert.-butylate were added all at once to a solution of 284.0 gm (1.23 mols) of 4-acetyl-2-chloro-biphenyl and 292.0 gm (1.85 mols) of ethyl (E)-3-ethoxy-crotonate in 1.8 liters of anhydrous dimethylformamide. The temperature rose at once from +20°C to +38°C, and the mixture turned red. The mixture was stirred for 1 hour at 32° to 35°C, then 200 ml of concentrated hydrochloric acid were added dropwise to the warm batch, and the resulting mixture was heated at a temperature of 90°-100°C for 30 minutes. After the carbon dioxide evolution had ceased, the cooled mixture was poured into 2 liters of ice water and extracted exhaustively with ether. The combined ether extracts were washed with water, with a saturated aqueous sodium bicarbonate solution and again with water, dried over sodium sulfate and evaporated. The oily residue was distilled in a moderate vacuum (b.p. 170°-175° C at 0.3 mm Hg) and subsequently recrystallized from cyclohexane and petroleum ether. 273.6 Gm (82% of theory) of pale yellow crystals, m.p. 66°-67°C, were obtained.

Workup

  1. customonce from +20°C to +38°C
  2. temperaturethe resulting mixture was heated at a temperature of 90°-100°C for 30 minutes
  3. extractionextracted exhaustively with ether
  4. washThe combined ether extracts were washed with water, with a saturated aqueous sodium bicarbonate solution and again with water
  5. dry with materialdried over sodium sulfate
  6. customevaporated
  7. distillationThe oily residue was distilled in a moderate vacuum (b.p. 170°-175° C at 0.3 mm Hg)
  8. customsubsequently recrystallized from cyclohexane and petroleum ether
  9. custom273.6 Gm (82% of theory) of pale yellow crystals, m.p. 66°-67°C, were obtained

Sources & evidence

ORD record
ord-6df0f44b8cd7473daf4ee45900ced120
Source dataset
uspto-grants-1976_04
Patent number
US03950427

Reaction notes

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