Water → 2-Cyclopropylethynylphenylamine

HRID 2278664Notes

Reaction equation

HRID 2278664 reaction equation
[CH:1]1([C:4]#[CH:5])[CH2:3][CH2:2]1.I[C:7]1[CH:13]=[CH:12][CH:11]=[CH:10][C:8]=1[NH2:9].CN(C)C=O.O>C(N(CC)CC)C.[Cu]I.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.C(OCC)(=O)C>[CH:1]1([C:4]#[C:5][NH:9][C:8]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:7]=2)[CH2:3][CH2:2]1

Participants

9

Reactant 4

HCID 962WaterHCID 6228Dimethylformamide2×HCID 119952-IodoanilineHCID 138823Cyclopropylacetylene

Product 1

HCID 682815352-Cyclopropylethynylphenylamine

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

0.26 g of copper(I) iodide, 0.30 g of bis(triphenylphosphine)palladium(II) dichloride and then 0.78 ml of cyclopropylacetylene are successively added to a solution of 1.0 g of 2-iodoaniline in 5 ml of triethylamine under argon. The reaction mixture is stirred at ambient temperature for 30 minutes, and then 1 ml of N,N-dimethylformamide is added. The reaction mixture is stirred at ambient temperature for 30 minutes, then 1 ml of N,N-dimethylformamide is again added. The reaction mixture is stirred at ambient temperature for 15 hours, and is then poured into 100 ml of water. After the addition of 50 ml of ethyl acetate, the mixture is filtered through Celite®, and then separated by settling out. The organic phase is separated and the aqueous phase is extracted with 3×40 ml of ethyl acetate. The organic phases are combined, washed with 2×40 ml of water, dried over anhydrous magnesium sulfate, filtered, and then concentrated to dryness under reduced pressure. The residue is purified on a 50 g column of 20-45 μm silica, elution being carried out with an 80/20 v/v dichloromethane/cyclohexane mixture. 0.42 g of 2-cyclopropylethynylphenylamine is thus obtained in the form of a brown oil which is used directly in the next step.

Workup

  1. stirringThe reaction mixture is stirred at ambient temperature for 30 minutes
  2. stirringThe reaction mixture is stirred at ambient temperature for 15 hours
  3. filtrationthe mixture is filtered through Celite®
  4. customseparated
  5. customThe organic phase is separated
  6. extractionthe aqueous phase is extracted with 3×40 ml of ethyl acetate
  7. washwashed with 2×40 ml of water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated to dryness under reduced pressure
  11. customThe residue is purified on a 50 g column of 20-45 μm silica, elution

Sources & evidence

ORD record
ord-b9a8005d09c7435d99d9afc5df415e5a
Source dataset
uspto-grants-2015_09
Patent number
US09133168B2

Reaction notes

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