Methyl 4-bromobenzoate → Methyl 4-trimethylsilylethynylbenzoate

HRID 1477232Notes

Reaction equation

HRID 1477232 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].Br[C:8]1[CH:17]=[CH:16][C:11]([C:12]([O:14][CH3:15])=[O:13])=[CH:10][CH:9]=1>[Cu]I>[CH3:4][Si:3]([C:1]#[C:2][C:8]1[CH:17]=[CH:16][C:11]([C:12]([O:14][CH3:15])=[O:13])=[CH:10][CH:9]=1)([CH3:6])[CH3:5]

Participants

4

Reactant 2

HCID 12081Methyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene

Product 1

HCID 640161Methyl 4-trimethylsilylethynylbenzoateYield 96%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
90 °C

Procedure

Ethynyltrimethylsilane (82.4 g, 0.84 mol) was added dropwise over 10 min under a nitrogen atmosphere to a solution of methyl 4-bromobenzoate (150 g, 0.7 mol), PdCl2 (PPh3)2 (15 g, 0.021 mol) and CuI (13 g, 0.07 mol) in TEA (1.5 L) and the reaction was stirred at 90° C. for 30 minutes. Solids were collected by filtration and washed with EtOAc (5×500 mL). The filtrate was concentrated under reduced pressure to give a residue, which was distilled under reduced pressure to yield methyl 4-((trimethylsilyl)ethynyl)benzoate (INT-1.2) as an off-white solid (156 g, 96%).

Workup

  1. filtrationSolids were collected by filtration
  2. washwashed with EtOAc (5×500 mL)
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customto give a residue, which
  5. distillationwas distilled under reduced pressure

Sources & evidence

ORD record
ord-39f91ea704b94d0d88d779f972f6c020
Source dataset
uspto-grants-2016_08
Patent number
US09403758B2

Reaction notes

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