Acetonitrile → HCID 136440582, compound

HRID 393904Notes

Reaction equation

HRID 393904 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[CH2:7]([C:9]1[C:13]2[N:14]=[C:15]([C:19]3[C:20]([O:26][CH2:27][CH2:28][CH3:29])=[N:21][CH:22]=[C:23](I)[CH:24]=3)[NH:16][C:17](=[O:18])[C:12]=2[N:11]([CH2:30][CH2:31][N:32]2[CH2:37][CH2:36][O:35][CH2:34][CH2:33]2)[N:10]=1)[CH3:8].C(#N)C>C(N(CC)CC)C.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>[CH2:7]([C:9]1[C:13]2[N:14]=[C:15]([C:19]3[C:20]([O:26][CH2:27][CH2:28][CH3:29])=[N:21][CH:22]=[C:23]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH:24]=3)[NH:16][C:17](=[O:18])[C:12]=2[N:11]([CH2:30][CH2:31][N:32]2[CH2:37][CH2:36][O:35][CH2:34][CH2:33]2)[N:10]=1)[CH3:8]

Participants

7

Reactant 3

HCID 6342AcetonitrileHCID 66111Trimethylsilylacetylene2×HCID 135673968HCID 135673968, compound

Product 1

HCID 136440582HCID 136440582, compoundYield 16.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

Trimethylsilylacetylene (0.39 mL, 2.79 mmol) was added to a solution of the title compound of example 5 (1.0 g, 1.86 mmol) in triethylamine (20 mL). Acetonitrile (1 mL), bis(triphenylphosphine)palladium (II) chloride (33 mg, 2.5 mol %), and copper (I) iodide (9 mg, 2.5 mol %) were added and the resultant mixture stirred at room temperature for 1 h after which further trimethylsilylacetylene (0.39 mL, 2.79 mmol) was added and the mixture stirred for 10 h. After removal of the solvent in vacuo, the residue was partitioned between ethyl acetate (25 mL) and water (20 mL), the aqueous phase separated and extracted with further ethyl acetate (3×25 mL). Combined organics were washed with brine (25 mL), dried over MgSO4, and concentrated to an oil which was crystallised from diisopropyl ether to afford the title compound as a white solid (156 mg, 0.30 mmol). The addition of pentane to the concentrated mother liquors afforded a second crop (509 mg, 1.0 mmol).

Workup

  1. additionwas added
  2. customAfter removal of the solvent in vacuo
  3. customthe residue was partitioned between ethyl acetate (25 mL) and water (20 mL)
  4. customthe aqueous phase separated
  5. extractionextracted with further ethyl acetate (3×25 mL)
  6. washCombined organics were washed with brine (25 mL)
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated to an oil which
  9. customwas crystallised from diisopropyl ether

Sources & evidence

ORD record
ord-81009c6704724a538638ed303f52e8fd
Source dataset
uspto-grants-2004_10
Patent number
US06809200B2

Reaction notes

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