Iodine → 1,1-Bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propene

HRID 1282459Notes

Reaction equation

HRID 1282459 reaction equation
[CH3:1][N:2]([CH3:22])[C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=[C:10](Br)[CH3:11])=[CH:5][CH:4]=1.[Mg].II.Cl[P:27]([C:32]([CH3:35])([CH3:34])[CH3:33])[C:28]([CH3:31])([CH3:30])[CH3:29]>[Cu](Cl)Cl.C(OCC)C.CCCCCCC.C1COCC1>[CH3:1][N:2]([CH3:22])[C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=[C:10]([P:27]([C:32]([CH3:35])([CH3:34])[CH3:33])[C:28]([CH3:31])([CH3:30])[CH3:29])[CH3:11])=[CH:5][CH:4]=1

Participants

9

Reactant 4

HCID 807IodineHCID 139566Di-tert-butylchlorophosphineHCID 5462224MagnesiumHCID 184244981,1-Bis(4-dimethylaminophenyl)-2-bromopropene

Product 1

HCID 120108281,1-Bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propeneYield 20%

Reagents, catalysts & solvents 4

HCID 24014Cupric ChlorideCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8900HeptaneSolvent

Procedure

Into a reactor were introduced 1.44 g (4.00 mmol) of the 1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4 (2), 0.107 g (4.4 mmol) of magnesium, and 11.5 mL of THF under a nitrogen atmosphere. A slight amount of iodine was added to the mixture to ascertain initiation of a reaction. Thereafter, the reaction mixture was refluxed for 2 hours and then cooled. Thereto were added 0.416 g (4.2 mmol) of copper chloride and 0.91 mL (4.4 mmol) of chlorodi-tert-butylphosphine. The reaction mixture was refluxed for 18 hours and then cooled to room temperature. Thereto were added 22.5 mL of heptane and 7.5 mL of diethyl ether. The crystals yielded were taken out by filtration and dissolved in 30 mL of ethyl acetate. The resultant solution was washed with 28% ammonia water and an aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol to obtain 0.34 g (20%) of the target compound as white crystals.

Workup

  1. custominitiation of a reaction
  2. temperatureThereafter, the reaction mixture was refluxed for 2 hours
  3. temperaturecooled
  4. temperatureThe reaction mixture was refluxed for 18 hours
  5. customThe crystals yielded
  6. filtrationwere taken out by filtration
  7. dissolutiondissolved in 30 mL of ethyl acetate
  8. washThe resultant solution was washed with 28% ammonia water
  9. dry with materialan aqueous sodium chloride solution and then dried with anhydrous magnesium sulfate
  10. customThereafter, the solvent was removed under reduced pressure
  11. customThe concentrate was recrystallized from ethanol

Sources & evidence

ORD record
ord-96f37795be044bbba9f6fa6009ca3034
Source dataset
uspto-grants-2002_09
Patent number
US06455720B1

Reaction notes

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