Triphenylphosphine → (3,5-Dimethyl-phenylethynyl)-trimethyl-silane

HRID 382899Notes

Reaction equation

HRID 382899 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH3:9])[CH:5]=[C:6]([CH3:8])[CH:7]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[CH3:29][Si:30]([C:33]#[CH:34])([CH3:32])[CH3:31]>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(NC(C)C)(C)C>[CH3:29][Si:30]([CH3:32])([CH3:31])[C:33]#[C:34][C:2]1[CH:3]=[C:4]([CH3:9])[CH:5]=[C:6]([CH3:8])[CH:7]=1

Participants

7

Reactant 3

HCID 11776Triphenylphosphine2×HCID 66111Trimethylsilylacetylene2×HCID 136357Benzene, 1-bromo-3,5-dimethyl-

Product 1

HCID 18362235(3,5-Dimethyl-phenylethynyl)-trimethyl-silane

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst2×HCID 178418476HCID 178418476, compoundCatalyst2×HCID 7912DiisopropylamineSolvent

Conditions

Temperature
75 °C

Procedure

A solution of 5-bromo-m-xylene (19.4 g, 105 mmol) and diisopropylamine (100 mL) was degassed with argon and kept under an argon atmosphere. CuI (2.07 g, 10.7 mmol), PPh3 (4.06 g, 15.3 mmol) and Pd(PPh3)2Cl2 (2.09 g, 2.92 mmol) were added followed by addition of trimethylsilylacetylene (12.3 g, 18 mL, 125 mmol). The reaction was heated to 75° C. for 2 h giving a dark brown viscous mixture. Additional trimethylsilylacetylene (6.15 g, 9 mL, 63 mmol), PPh3 (2.04 g, 7.78 mmol), CuI (1.05 g, 5.51 mmol) and Pd(PPh3)2Cl2 (1.62 g, 2.31 mmol) were added and then the reaction was heated to 80° C. for 4 h. After cooling the reaction to room temperature, hexanes (300 mL) was added and the solution was filtered through celite. The hexane layer was washed with 1N HCl (600 mL), brine (300 mL), dried (Na2SO4), and concentrated to give crude 1-trimethylsilyl-2-(3,5-dimethylphenyl)-acetylene which was used for the next step.

Workup

  1. customgiving a dark brown viscous mixture
  2. temperaturethe reaction was heated to 80° C. for 4 h
  3. temperatureAfter cooling
  4. customthe reaction to room temperature
  5. filtrationthe solution was filtered through celite
  6. washThe hexane layer was washed with 1N HCl (600 mL), brine (300 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-b5433b00e00d4f05b020496bda33bf60
Source dataset
uspto-grants-2001_10
Patent number
US06310247B1

Reaction notes

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