Triethylamine → 3-(2-Trimethylsilylethynylphenyl)urea

HRID 530432Notes

Reaction equation

HRID 530432 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]([NH2:11])=[O:10].[C:12]([Si:14]([CH3:17])([CH3:16])[CH3:15])#[CH:13].C(N(CC)CC)C>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:15][Si:14]([C:12]#[C:13][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]([NH2:11])=[O:10])([CH3:17])[CH3:16]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 139387Urea, (2-iodophenyl)-

Product 1

HCID 112992393-(2-Trimethylsilylethynylphenyl)ureaYield 90%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

To a degassed solution of 1-(2-iodophenyl)urea (2.62 g, 10 mmol, 1 eq), ethynyltrimethyl silane (4.16 mL, 3 eq), and triethylamine (5.58 mL, 4 eq) in anhydrous DMF (15 mL) was added bis(triphenylphosphine)palladium(II) dichloride (702 mg, 0.1 eq) and copper(I) iodide (190.4 mg, 0.1 eq). After the reaction mixture was stirred at room temperature for 30 minutes, it was partitioned between aqueous ammonium chloride and ethyl acetate. The organic layer was isolated, washed further with saturated sodium bicarbonate, brine, and lastly dried with sodium sulfate. The upper solution was decanted, concentrated, and the brown solid residue was treated with a small amount of DCM. The mixture was stirred at room temperature for 30 minute and filtered to obtain 1-{2-[(trimethylsilyl)ethynyl]phenyl}urea as a white solid in 1.645 g. The filtrate was concentrated and the residue was subject to a gradient column chromatography (EtOAc-hex from 1:100 to 1:1) to render 1-{2-[(trimethylsilyl)ethynyl]phenyl}urea with a second crop of 0.432 g in a total yield of 90%.

Workup

  1. customit was partitioned between aqueous ammonium chloride and ethyl acetate
  2. customThe organic layer was isolated
  3. washwashed further with saturated sodium bicarbonate, brine
  4. dry with materiallastly dried with sodium sulfate
  5. customThe upper solution was decanted
  6. concentrationconcentrated
  7. additionthe brown solid residue was treated with a small amount of DCM
  8. stirringThe mixture was stirred at room temperature for 30 minute
  9. filtrationfiltered

Sources & evidence

ORD record
ord-318f10ba2c6c40239a0cd76ef4c9f73c
Source dataset
uspto-grants-2016_05
Patent number
US09353093B2

Reaction notes

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