1,2-Epoxybutane → HCID 14372188, compound

HRID 1382902Notes

Reaction equation

HRID 1382902 reaction equation
P(Br)(Br)Br.[C:5]([N:8]1[C:17]2[C:12](=[CH:13][C:14]([CH:18](O)[CH3:19])=[CH:15][CH:16]=2)[C:11]([CH3:22])([CH3:21])[CH2:10][CH2:9]1)(=[O:7])[CH3:6].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[PH4+].[CH:43]([C:45]1[CH:54]=[CH:53][C:48]([C:49]([O:51][CH3:52])=[O:50])=[CH:47][CH:46]=1)=O.O1C(CC)C1>N1C=CC=CC=1.CCOCC>[C:5]([N:8]1[C:17]2[C:12](=[CH:13][C:14](/[C:18](/[CH3:19])=[CH:43]/[C:45]3[CH:54]=[CH:53][C:48]([C:49]([O:51][CH3:52])=[O:50])=[CH:47][CH:46]=3)=[CH:15][CH:16]=2)[C:11]([CH3:21])([CH3:22])[CH2:10][CH2:9]1)(=[O:7])[CH3:6]

Participants

9

Reactant 6

HCID 78341,2-EpoxybutaneHCID 11776TriphenylphosphineHCID 15294Methyl 4-FormylbenzoateHCID 24614Phosphorus tribromideHCID 5460504PhosphoniumHCID 14372187HCID 14372187, compound

Product 1

HCID 14372188HCID 14372188, compound

Reagents, catalysts & solvents 2

HCID 1049PyridineCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

Two drops of pyridine, followed by 3.28 g (0.012 mol) of phosphorus tribromide in 20 ml of ether, were added to 6.0 g (0.024 mol) of N-acetyl-4,4-dimethyl-6-(1-hydroxyethyl)-1,2,3,4-tetrahydroquinoline in 75 ml of ether, at 0° C., with stirring. Stirring was continued for 1 hour at 0° C., and then the reaction mixture was poured onto 100 g of ice. The resulting mixture was extracted with ether and the combined extracts were dried (MgSO4) and then evaporated in vacuo. This gave 7.0 g of a white solid which was dissolved in 100 ml of toluene. To the resulting solution ws added 12.6 g (0.048 mol) triphenylphosphine, and then the mixture was refluxed for 18 hours, during which time the phosphonium salt precipitated as a viscous oil. The solvent was decanted from the oil, and then the latter was triturated under hot toluene. The toluene was removed by decantation, the residue was dissolved in dichloromethane, the dichloromethane was dried, and then the dichloromethane was removed by evaporation in vacuo. The residue (7.5 g, 0.013 mol), 2.15 g of methyl 4-formylbenzoate and 75 ml of 1,2-epoxybutane were heated under reflux for 48 hours. The reaction mixture was then evaporated in vacuo to give the title compound in admixture with the corresponding (Z)-isomer. The isomers were separated by column chromatography on silicic acid, eluting with etherhexane (1:1 by volume). The (E)-isomer (2.8 g) was further purified by recrystallization from etherhexane to give 2.3 g (25% yield) of the title compound, mp 141°-142° C.

Workup

  1. stirringStirring
  2. extractionThe resulting mixture was extracted with ether
  3. dry with materialthe combined extracts were dried (MgSO4)
  4. customevaporated in vacuo
  5. dissolutionThis gave 7.0 g of a white solid which was dissolved in 100 ml of toluene
  6. customprecipitated as a viscous oil
  7. customThe solvent was decanted from the oil
  8. customthe latter was triturated under hot toluene
  9. customThe toluene was removed by decantation
  10. dissolutionthe residue was dissolved in dichloromethane
  11. dry with materialthe dichloromethane was dried
  12. customthe dichloromethane was removed by evaporation in vacuo
  13. temperatureunder reflux for 48 hours
  14. customThe reaction mixture was then evaporated in vacuo

Sources & evidence

ORD record
ord-3caf0ffe964d435d99b7f1143d8fc765
Source dataset
uspto-grants-1989_02
Patent number
US04808597

Reaction notes

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