Water → Ethyl 4-((trimethylsilyl)ethynyl)benzoate

HRID 1281229Notes

Reaction equation

HRID 1281229 reaction equation
Br[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15].C(NCC)C.O>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I.CCOCC>[CH3:13][Si:14]([C:17]#[C:18][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1)([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 962WaterHCID 8021DiethylamineHCID 22043Ethyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene

Product 1

HCID 10729134Ethyl 4-((trimethylsilyl)ethynyl)benzoate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

A resealable tube was flame-dried under high vacuum. The vacuum was broken by the addition of dry argon, and the flask was allowed to cool to room temperature. The flask was charged with 5.0 g (18.1 mmol) of ethyl 4-bromobenzoate, 7.7 mL (54.3 mmol) of (trimethylsilyl)acetylene, and 65 mL of diethylamine. The solution was purged with argon for 15 minutes and bis(triphenylphosphine)palladium (II) chloride (320 mg, 0.45 mmol) and copper (I) iodide (87 mg, 0.45 mmol) were added, the tube sealed, and the solution stirred at 55° C. for 3 days. The solution was poured into a separatory funnel containing water and ether. The layers were separated and the aqueous layer was extracted 3 times with ether. The combined ether layers were washed once with brine, and dried over magnesium sulfate, and the solvents were removed under reduced pressure. The residue was purified by silica gel chromatography (95:5. hexane:ethyl acetate) to give the title compound.

Workup

  1. customA resealable tube was flame-dried under high vacuum
  2. additionThe vacuum was broken by the addition of dry argon
  3. customThe solution was purged with argon for 15 minutes
  4. customthe tube sealed
  5. additionThe solution was poured into a separatory funnel
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted 3 times with ether
  8. washThe combined ether layers were washed once with brine
  9. dry with materialdried over magnesium sulfate
  10. customthe solvents were removed under reduced pressure
  11. customThe residue was purified by silica gel chromatography (95:5. hexane:ethyl acetate)

Sources & evidence

ORD record
ord-e4a72f9a600b4cfe90c5080d421b6d47
Source dataset
uspto-grants-2002_09
Patent number
US06452032B1

Reaction notes

Loading…