Triphenylphosphine → Methyl 4-trimethylsilylethynylbenzoate

HRID 861763Notes

Reaction equation

HRID 861763 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 of 400 mg of triphenylphosphine were introduced into a three-necked flask under a stream of nitrogen. 20 g (0.204 mol) of trimethylsilylacetylene were then added, the mixture was heated progressively to 90° C. over 1 hour and maintained at this temperature for 5 hours. The reaction mixture was cooled, the salt filtered and evaporated. The residue was taken up with 200 ml of hydrochloric acid (5%) and 400 ml of ethyl ether. The ether phase was separated by settling, washed with water, dried over magnesium sulfate and evaporated. The residue obtained was purified by chromatography on a silica column diluted with dichloromethane. After the evaporation of the solvents, 23 g (100%) of the expected compound were recovered in the form of a colorless oil.

Workup

  1. temperaturemaintained at this temperature for 5 hours
  2. temperatureThe reaction mixture was cooled
  3. filtrationthe salt filtered
  4. customevaporated
  5. customThe ether phase was separated
  6. washwashed with water
  7. dry with materialdried over magnesium sulfate
  8. customevaporated
  9. customThe residue obtained
  10. customwas purified by chromatography on a silica column
  11. additiondiluted with dichloromethane
  12. customAfter the evaporation of the solvents, 23 g (100%) of the expected compound
  13. customwere recovered in the form of a colorless oil

Sources & evidence

ORD record
ord-b95d466d8d714ba18023176de32a678f
Source dataset
uspto-grants-1998_02
Patent number
US05716624

Reaction notes

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