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

HRID 1247704Notes

Reaction equation

HRID 1247704 reaction equation
Cl[C:2]1([CH3:17])[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:24]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:25]([CH3:28])([CH3:27])[CH3:26]>CCCCCC.[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:24]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:25]([CH3:28])([CH3:27])[CH3:26])[CH3:17])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

9

Reactant 5

HCID 807IodineHCID 82050Lithium BromideHCID 139566Di-tert-butylchlorophosphineHCID 5462224MagnesiumHCID 128696081-Chloro-1-methyl-2,2-diphenylcyclopropane

Product 1

HCID 21909131Di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphaneYield 25.2%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
60 °C

Procedure

Under a nitrogen atmosphere, 1-chloro-1-methyl-2,2-diphenylcyclopropane (2.43 g, 10.0 mmol), magnesium (0.279 g, 11.5 mmol) and THF (10 ml) were placed in a reaction flask, followed by addition of a trace amount of iodine and stirring at 60° C. for 5 hours. After cooling, copper iodide (1.92 g, 10.0 mmol), lithium bromide (0.879 g, 10.1 mmol) and chlorodi-tert-butylphosphine (2.1 ml, 11.0 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% (w/w) aqueous ammonia and a brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title compound (0.89 g, 25%) 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% (w/w) aqueous ammonia
  8. dry with materiala brine, and dried over anhydrous magnesium sulfate
  9. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-9094c94026fc4014a56e9606ac7fa179
Source dataset
uspto-grants-2006_10
Patent number
US07129367B2

Reaction notes

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