Water → 5-Trifluoromethyl-2-trimethylsilanylethynylphenylamine

HRID 1666808Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1666808
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

Komponenten

8

Edukt 4

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

Produkt 1

HCID 534238715-Trifluoromethyl-2-trimethylsilanylethynylphenylamine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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)+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-9f9c26ccfa9343b6b27017835a1503d1
Quelldatensatz
uspto-grants-2011_10
Patentnummer
US08044090B2

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