Water → 5-Trifluoromethyl-2-trimethylsilanylethynylphenylamine

HRID 1371867Notes

Reaction equation

HRID 1371867 reaction equation
C(O[C:4](=O)[NH:5][C:6]1[CH:11]=[C:10]([C:12]([F:15])([F:14])[F:13])[CH:9]=[CH:8][C:7]=1Br)C.C(N(CC)CC)C.[CH3:25][Si:26]([C:29]#C)([CH3:28])[CH3:27].O>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.CCOCC>[F:13][C:12]([F:15])([F:14])[C:10]1[CH:9]=[CH:8][CH:7]=[C:6]([NH:5][C:4]#[C:25][Si:26]([CH3:29])([CH3:28])[CH3:27])[CH:11]=1

Participants

8

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 11738467N-(2-bromo-5-trifluoromethylphenyl)carbamic acid ethyl ester

Product 1

HCID 534238715-Trifluoromethyl-2-trimethylsilanylethynylphenylamine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

Following the procedure described in J. Org. Chem. 1997, 62, 6507, combine N-(2-bromo-5-trifluoromethylphenyl)carbamic acid ethyl ester (34.33 g, 110 mmol), triethylamine (300 mL), dichlorobis(triphenylphosphine)palladium(II) (5.4 g, 7.7 mmol), and copper (I) iodide (1.47 g, 7.7 mmol). Evacuate the dark solution and fill with N2 twice and then quickly add (trimethylsilyl)acetylene (16.21 g, 165 mmol, 23.32 mL) with vigorous stirring. Heat to 80° C. When TLC indicates absence of the starting material, add water and Et2O and filter through celite and evaporate the filtrate in vacuo to give a residue. Dilute residue with water and extract with Et2O, combine the organic layers and remove the evaporate to give a dark brown oil. Absorb the oil onto silica gel and load onto a short column of silica gel equilibrated with 100% hexanes. Wash with 100% hexanes (2 L) and elute the product with 1% EtOAc in hexanes. Pool fractions containing the product and remove in vacuo the solvent to give 5-trifluoromethyl-2-trimethylsilanylethynyl phenylamine as a red/brown oil; MS (IS): m/z 330 (M+H)+.

Workup

  1. customEvacuate the dark solution and fill with N2 twice
  2. filtrationfilter through celite
  3. customevaporate the filtrate in vacuo
  4. customto give a residue
  5. extractionDilute residue with water and extract with Et2O
  6. customremove the
  7. customevaporate
  8. customto give a dark brown oil
  9. customAbsorb the oil onto silica gel and load onto a short column of silica gel
  10. washWash with 100% hexanes (2 L)
  11. washelute the product with 1% EtOAc in hexanes
  12. additionPool fractions containing the product
  13. customremove in vacuo the solvent

Sources & evidence

ORD record
ord-c4f17e94d76543c4b25409c9bce802ac
Source dataset
uspto-grants-2007_01
Patent number
US07157488B2

Reaction notes

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