Triphenylphosphine → Methyl 4-trimethylsilylethynylbenzoate

HRID 2415232Notes

Reaction equation

HRID 2415232 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 are introduced into a three-necked flask. 20 g (0.204 mol) of trimethylsilylacetylene are then added, after which the mixture is heated gradually to 90° C. over 1 hour and left at this temperature for 5 hours. The reaction medium is then cooled, the salt is filtered of and the filtrate is evaporated. The residue is taken up in 200 ml of hydrochloric acid (5%) and 400 ml of ethyl ether. The ether phase is separated out after settling has taken place, washed with water, dried over magnesium sulphate and evaporated. The residue obtained is purified by chromatography on a column of silica eluted with dichloromethane. After evaporation of the solvents, 23 g (100%) of the expected derivative are collected in the form of a colourless oil.

Workup

  1. additionare introduced into a three-necked flask
  2. temperatureThe reaction medium is then cooled
  3. filtrationthe salt is filtered of and the filtrate
  4. customis evaporated
  5. customThe ether phase is separated out after settling
  6. washwashed with water
  7. dry with materialdried over magnesium sulphate
  8. customevaporated
  9. customThe residue obtained
  10. customis purified by chromatography on a column of silica
  11. washeluted with dichloromethane
  12. customAfter evaporation of the solvents, 23 g (100%) of the expected derivative
  13. customare collected in the form of a colourless oil

Sources & evidence

ORD record
ord-325e9326b4c34691894453492422a0fc
Source dataset
uspto-grants-2004_11
Patent number
US06818666B2

Reaction notes

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