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Iodine → Bis(1,1-dimethylethyl)(1-methyl-2,2-diphenylethenyl)phosphine

HRID 1282454
Notes
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Reaction equation

HRID 1282454 reaction equation
[C:1]1([C:7]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:8](P(C2C=CC=CC=2)C2C=CC=CC=2)[CH3:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Mg].II.BrC1C=CC=CC=1.Cl[P:40]([C:45]([CH3:48])([CH3:47])[CH3:46])[C:41]([CH3:44])([CH3:43])[CH3:42]>[Cu](Cl)Cl.CCCCCCC.C1COCC1>[C:1]1([C:7]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)=[C:8]([P:40]([C:45]([CH3:48])([CH3:47])[CH3:46])[C:41]([CH3:44])([CH3:43])[CH3:42])[CH3:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 5

HCID 807IodineHCID 7961BromobenzeneHCID 139566Di-tert-butylchlorophosphineHCID 5462224MagnesiumHCID 120108231,1-Diphenyl-2-(diphenylphosphino)propene

Product 1

HCID 12010825Bis(1,1-dimethylethyl)(1-methyl-2,2-diphenylethenyl)phosphineYield 43.5%

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 8028TetrahydrofuranSolventHCID 8900HeptaneSolvent

Procedure

Into a reactor were introduced 1.37 g (5.0 mmol) of the 2-bromo-11-diphenylpropene obtained in Example 1 (2), 0.134 g (5.5 mmol) of magnesium, and 11 mL of THF under a nitrogen atmosphere. Iodine and bromobenzene were added to the mixture in a slight amount to ascertain initiation of a reaction. Thereafter, the reaction mixture was refluxed for 2 hours and then cooled. Thereto were added 0.520 g (5.3 mmol) of copper chloride and 1.1 mL (5.5 mmol) of chlorodi-t-butylphosphine. This reaction mixture was refluxed for 18 hours and then cooled to room temperature. Thereto was added 14 mL of heptane. The crystals yielded were taken out by filtration and dissolved in 40 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 0.736 g (43%) 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. temperatureThis reaction mixture was refluxed for 18 hours
  5. customThe crystals yielded
  6. filtrationwere taken out by filtration
  7. dissolutiondissolved in 40 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-a863d69d3db4422399910c6a7a8a89b5
Source dataset
uspto-grants-2002_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06455720B1

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes