Acetic acid, 2-(triphenylphosphoranylidene)-, methyl ester → HCID 86586485, compound

HRID 394703Notes

Reaction equation

HRID 394703 reaction equation
[CH2:1]([CH:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6][C:5]1=O)[CH:2]=[CH2:3].C1(P(=[CH:40][C:41]([O:43][CH3:44])=[O:42])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.ClCCl>[CH2:1]([CH:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6][C:5]1=[CH:40][C:41]([O:43][CH3:44])=[O:42])[CH:2]=[CH2:3]

Participants

5

Reactant 2

HCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 22643872HCID 22643872, compound

Product 1

HCID 86586485HCID 86586485, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

A solution containing 16.3 g of (4RS)-4-allyl-1-benzyloxycarbonylpiperidin-3-one in 200 cm3 of toluene was stirred under reflux with methyl (triphenylphosphoranylidene)acetate, under an inert atmosphere, for 16 hours. After cooling to about 20° C., the reaction mixture was concentrated under reduced pressure (5 kPa) at a temperature in the region of 40° C., the residue obtained, solubilized in 50 cm3 of dichloromethane in the hot state, was purified by chromatography, under a nitrogen pressure of 50 kPa, on a column of silica gel (particle size 20-45 μ; diameter 10 cm; height 45 cm), eluting with a cyclohexane-ethyl acetate (80/20 by volume) mixture. 250-cm3 fractions were collected. Fractions 13 to 15 were combined and then concentrated as above. 5.8 g of methyl (4RS)-4-allyl-1-benzyloxycarbonylpiperidin-3-ylidenacetate (Z isomer) were obtained in the form of a colorless oil.

Workup

  1. concentrationthe reaction mixture was concentrated under reduced pressure (5 kPa) at a temperature in the region of 40° C.
  2. customthe residue obtained
  3. customwas purified by chromatography, under a nitrogen pressure of 50 kPa
  4. washon a column of silica gel (particle size 20-45 μ; diameter 10 cm; height 45 cm), eluting with a cyclohexane-ethyl acetate (80/20 by volume) mixture
  5. custom250-cm3 fractions were collected
  6. concentrationconcentrated as above

Sources & evidence

ORD record
ord-6d1093a3c23b4bbc806d3faf5143f59f
Source dataset
uspto-grants-2003_08
Patent number
US06602884B2

Reaction notes

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