Triphenylphosphine → HCID 22376413, compound

HRID 620097Notes

Reaction equation

HRID 620097 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9](C)(C)[CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH3:15][Si:16](C#C)([CH3:18])[CH3:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.C(Cl)Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:15][Si:16]([C:10]#[C:9][O:8][C:6](=[O:7])[C:5]1[CH:13]=[CH:14][CH:2]=[CH:3][CH:4]=1)([CH3:18])[CH3:17]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 11334366Tert-butyl 4-bromobenzoate

Product 1

HCID 22376413HCID 22376413, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
100 °C

Procedure

A mixture containing 1.31 g of tert.-butyl 4-bromobenzoate, 1.0 g of trimethylsilylacetylene, 10 mg of palladium acetate and 15.6 mg of triphenylphosphine in 15 ml of anhydrous triethylamine is heated in a sealed container at 100° C. for 16 hours. After cooling to room temperature, the reaction mixture is diluted with methylene chloride and extracted with water. The organic solution is dried over anhydrous sodium sulfate and the solvent removed under reduced pressure. The dark residue is chromatographed as a column of flash silica gel using a 10% ethyl acetate-hexanes mixture as the eluent to give tert.-butyl 4-(trimethylsilylethynylbenzoate as a dark oil: NMR (CDCl3, 300 MHz) delta 0.26 (s, 9H), 1.59 (s, 9H), 7.49 (d, 2H, J=8.23 Hz), 7.91 (d, 2H, J8.23 Hz). This is dissolved in 20 ml of anhydrous methanol, and then treated with 0.1 g of anhydrous potassium carbonate. The mixture is allowed to stir at room temperature under nitrogen for 3 hours. The reaction mixture is diluted with methylene chloride, extracted with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue is distilled under reduced pressure (60°-70° C./0.1 mm to give 0.75 g (73% over 2 steps) of tert.-butyl 4-ethynylbenzoate as a white solid: m.p. 71.5°-72° C.; NMR (CDCl3, 80 MHz) delta 1.62 (s, 9H), 3.23 (s, 1H), 7.55 (d, 2H, J=8.11 Hz), 7.96 (d, 2H, J=8.11 Hz); IR (KBr) 3240, 2970, 2100, 1700, 1600, 1450, 1365, 1300, 1250, 1160, 1115, 1015, 845 and 765 cm-1 ; M/S 202 M+), 187, 157, 146, 129, 101, 75 and 57.

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionextracted with water
  3. dry with materialThe organic solution is dried over anhydrous sodium sulfate
  4. customthe solvent removed under reduced pressure
  5. customThe dark residue is chromatographed as a column of flash silica gel using a 10% ethyl acetate-hexanes mixture as the eluent

Sources & evidence

ORD record
ord-3a16239c2ee348ebbb3a3d52efe6f77a
Source dataset
uspto-grants-1989_04
Patent number
US04818819

Reaction notes

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