Triphenylphosphine → Methyl 4-trimethylsilylethynylbenzoate

HRID 1957689Notes

Reaction equation

HRID 1957689 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:31][Si:32]([C:35]#[CH:36])([CH3:34])[CH3:33]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(N(CC)CC)C>[CH3:31][Si:32]([C:35]#[C:36][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1)([CH3:34])[CH3:33]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 12081Methyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene

Product 1

HCID 640161Methyl 4-trimethylsilylethynylbenzoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
90 °C

Procedure

21.5 g (0.1 mol) of methyl 4-bromobenzoate, 300 ml of triethylamine and a mixture of 200 mg of palladium acetate and 400 mg of triphenylphosphine were introduced into a three-necked flask under a stream of nitrogen. 20 g (0.204 mmol) of trimethylsilylacetylene were then added and the mixture was heated gradually to 90° C. over 1 hour and maintained at this temperature for 5 hours. The reaction medium was cooled, the salt was filtered off and the filtrate was evaporated. The residue was taken up in 200 ml of hydrochloric acid (5%) and 400 ml of ethyl ether. The ether phase was separated out after settling had taken place, washed with water, dried over magnesium sulfate and evaporated. The residue obtained was purified by chromatography on a column of silica, eluted with dichloromethane. After evaporation of the solvents, 23 g (100%) of the compound were recovered in the form of a colorless oil.

Workup

  1. additionwere introduced into a three-necked flask under a stream of nitrogen
  2. temperaturemaintained at this temperature for 5 hours
  3. temperatureThe reaction medium was cooled
  4. filtrationthe salt was filtered off
  5. customthe filtrate was evaporated
  6. customThe ether phase was separated out
  7. washwashed with water
  8. dry with materialdried over magnesium sulfate
  9. customevaporated
  10. customThe residue obtained
  11. customwas purified by chromatography on a column of silica
  12. washeluted with dichloromethane
  13. customAfter evaporation of the solvents, 23 g (100%) of the compound
  14. customwere recovered in the form of a colorless oil

Sources & evidence

ORD record
ord-31ef0623b9cc4c5aae5b1dc6677f8c22
Source dataset
uspto-grants-1998_07
Patent number
US05786379

Reaction notes

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