Triphenylphosphine → 3,3',5,5'-Tetramethyl-7,7'-bis[3,5-bis(trimethylsilylethynyl)phenyl]-1,1'-biadamantane

HRID 39117Notes

Reaction equation

HRID 39117 reaction equation
[CH3:1][C:2]12[CH2:12][C:6]3([C:13]4[CH:18]=[C:17](Br)[CH:16]=[C:15](Br)[CH:14]=4)[CH2:7][C:8]([CH3:11])([CH2:10][C:4]([C:21]45[CH2:38][C:25]6([CH3:39])[CH2:26][C:27]([C:30]7[CH:35]=[C:34](Br)[CH:33]=[C:32](Br)[CH:31]=7)([CH2:29][C:23]([CH3:40])([CH2:24]6)[CH2:22]4)[CH2:28]5)([CH2:5]3)[CH2:3]1)[CH2:9]2.C1(P([C:54]2[CH:59]=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:60][Si:61]([C:64]#[CH:65])([CH3:63])[CH3:62]>[Cu](I)I.C(N(CC)CC)C>[CH3:1][C:2]12[CH2:12][C:6]3([C:13]4[CH:18]=[C:17]([C:65]#[C:64][Si:61]([CH3:63])([CH3:62])[CH3:60])[CH:16]=[C:15]([C:65]#[C:64][Si:61]([CH3:63])([CH3:62])[CH3:60])[CH:14]=4)[CH2:7][C:8]([CH3:11])([CH2:10][C:4]([C:21]45[CH2:38][C:25]6([CH3:39])[CH2:26][C:27]([C:30]7[CH:35]=[C:34]([C:65]#[C:64][Si:61]([CH3:63])([CH3:62])[CH3:60])[CH:33]=[C:32]([C:54]#[C:59][Si:61]([CH3:63])([CH3:62])[CH3:60])[CH:31]=7)([CH2:29][C:23]([CH3:40])([CH2:24]6)[CH2:22]4)[CH2:28]5)([CH2:5]3)[CH2:3]1)[CH2:9]2

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 575583803,3',5,5'-Tetramethyl-7,7'-bis(3,5-dibromophenyl)-1,1'-biadamantane

Product 1

HCID 575583753,3',5,5'-Tetramethyl-7,7'-bis[3,5-bis(trimethylsilylethynyl)phenyl]-1,1'-biadamantane

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
75 °C

Procedure

Next, 50 g (62.9 mmol) of the previously obtained 3,3′,5,5′-tetramethyl-7,7′-bis(3,5-dibromophenyl)-1,1′-biadamantane, 3.53 g (5.0 mmol) of dichlorobistriphenylphosphinepalladium, 6.60 g (25.2 mmol) of triphenylphosphine, 4.79 g (25.2 mmol) of copper(II) iodide and 750 ml of triethylamine were added to a flask and stirred. The mixture was raised to 75° C., and then 37.1 g (377.7 mmol) of trimethylsilylacetylene was slowly added. After stirring at 75° C. for 7 hours, the temperature was raised to 120° C. to remove the triethylamine. After returning to room temperature, 1000 ml of dichloromethane was added to the reaction mixture and stirring was continued for 20 minutes. The precipitate was removed by filtration, and 1000 ml of a 5% hydrochloric acid aqueous solution was added to the filtrate for liquid separation. The organic layer was washed three times with 1000 ml of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in 1500 ml of hexane. The insoluble portion was removed by filtration and the hexane in the filtrate was removed under reduced pressure. After introducing 1000 ml of acetone thereinto, the precipitate was washed 3 times with acetone to obtain 43 g of 3,3′,5,5′-tetramethyl-7,7′-bis[3,5-bis(trimethylsilylethynyl)phenyl]-1,1′-biadamantane.

Workup

  1. stirringAfter stirring at 75° C. for 7 hours
  2. temperaturethe temperature was raised to 120° C.
  3. customto remove the triethylamine
  4. customAfter returning to room temperature
  5. addition1000 ml of dichloromethane was added to the reaction mixture
  6. stirringstirring
  7. customThe precipitate was removed by filtration, and 1000 ml of a 5% hydrochloric acid aqueous solution
  8. additionwas added to the filtrate for liquid separation
  9. washThe organic layer was washed three times with 1000 ml of water
  10. customthe solvent of the organic layer was removed under reduced pressure
  11. dissolutionThe obtained compound was dissolved in 1500 ml of hexane
  12. customThe insoluble portion was removed by filtration
  13. customthe hexane in the filtrate was removed under reduced pressure
  14. additionAfter introducing 1000 ml of acetone
  15. washthe precipitate was washed 3 times with acetone

Sources & evidence

ORD record
ord-0525611debbf485db308abbbef8e01de
Source dataset
uspto-grants-2013_09
Patent number
US08524847B2

Reaction notes

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