Triphenylphosphine → Ethyl 3-oxo-4-(triphenyl-lambda~5~-phosphanylidene)butanoate

HRID 1942577Notes

Reaction equation

HRID 1942577 reaction equation
[C:1]1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[CH2:21][C:22](=[O:29])[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]>C1COCC1.O>[O:29]=[C:22]([CH:21]=[P:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 2734128Ethyl 3-oxo-4-(triphenyl-lambda~5~-phosphanylidene)butanoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

triphenylphosphine (30.0 g, 114.3 mmol) is added, at ambient temperature, to a solution of commercial ethyl 4-chloro-3-oxobutanoate (18.81 g, 114.3 mmol) in 200 mL of anhydrous THF. The reaction medium is taken to reflux for 18 h before being concentrated under vacuum. The oil obtained is taken up in distilled water then washed with ether. The aqueous phase is then basified by a saturated aqueous solution of NaHCO3 (up to pH 8). After extraction with AcOEt, the organic phases are combined, dried over MgSO4, filtered then concentrated under vacuum. Purification is carried out by recrystallization from ether in order to produce, after filtration and drying, compound 5′-2 (14.96 g, 38.0 mmol, 34%) in the form of a slightly yellow solid.

Workup

  1. temperatureto reflux for 18 h
  2. concentrationbefore being concentrated under vacuum
  3. customThe oil obtained
  4. washthen washed with ether
  5. extractionAfter extraction with AcOEt
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationthen concentrated under vacuum
  9. customPurification
  10. customis carried out by recrystallization from ether in order
  11. customto produce
  12. filtrationafter filtration
  13. customdrying

Sources & evidence

ORD record
ord-04ebc7b476524b1bb2e31b66601f3e78
Source dataset
uspto-grants-2013_03
Patent number
US08389569B2

Reaction notes

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