Iodine → Di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane

HRID 1247702

Reaction equation

HRID 1247702 reaction equation
Br[CH:2]1[CH2:4][C:3]1([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[Mg].II.[Br-].[Li+].Cl[P:23]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:24]([CH3:27])([CH3:26])[CH3:25].[CH3:32]CCCCC>[Cu](I)I.C1COCC1>[C:5]1([C:3]2([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[CH2:4][C:2]2([P:23]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:32])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

9

Reactant 6

HCID 807IodineHCID 8058HexaneHCID 82050Lithium BromideHCID 139566Di-tert-butylchlorophosphineHCID 282328(2-Bromo-1-phenylcyclopropyl)benzeneHCID 5462224Magnesium

Product 1

HCID 21909131Di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphaneYield 47%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

Under a nitrogen atmosphere, 1-bromo-2,2-diphenyl-cyclopropane (1.44 g, 5.0 mmol), magnesium (0.134 g, 5.5 mmol) and THF (10 ml) were placed in a reaction flask, followed by addition of a trace amount of iodine and stirring at 40° C. for one hour. After cooling, copper iodide (0.962 g, 5.0 mmol), lithium bromide (0.567 g, 6.5 mmol) and chlorodi-tert-butylphosphine (0.95 ml, 5.0 mmol) were added and the resulting mixture was stirred at 60° C. for 3 hours, followed by cooling to room temperature. The resulting mixture was diluted with hexane (20 ml) and crystal separated was collected by filtration. The crystal was dissolved in toluene, and the toluene solution was washed with a 28% aqueous ammonia and a brine, and dried over anhydrous magnesium sulfate. The solvent was then removed under reduced pressure to give the title compound (0.83 g, 47%) as white crystal.

Workup

  1. temperatureAfter cooling
  2. stirringthe resulting mixture was stirred at 60° C. for 3 hours
  3. temperatureby cooling to room temperature
  4. customseparated
  5. filtrationwas collected by filtration
  6. dissolutionThe crystal was dissolved in toluene
  7. washthe toluene solution was washed with a 28% aqueous ammonia
  8. dry with materiala brine, and dried over anhydrous magnesium sulfate
  9. customThe solvent was then removed under reduced pressure

Sources & evidence

ORD record
ord-aec168b5a6f641b3bf59928e3e57392e
Source dataset
uspto-grants-2006_10
Patent number
US07129367B2

Linked notes

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