Triphenylphosphine → 2-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

HRID 1443110Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1443110
Br[C:2]1[S:6][C:5]([CH3:7])=[N:4][C:3]=1[C:8]#[N:9].[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.O.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>[CH3:7][C:5]1[S:6][C:2]([C:15]#[C:14][Si:11]([CH3:13])([CH3:12])[CH3:10])=[C:3]([C:8]#[N:9])[N:4]=1

Komponenten

8

Edukt 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 8493835-Bromo-2-methylthiazole-4-carbonitrile

Produkt 1

HCID 685385072-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 962WaterLösungsmittelHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

5-Bromo-2-methyl-thiazole-4-carbonitrile (4.8 g, 23.6 mmol) was suspended in 50 ml triethyl amine. Trimethylsilylacetylene (4.64 g, 47.3 mmol), triphenylphosphine (186 mg, 0.7 mmol) and bis(triphenylphosphine)palladium(II)chloride (0.83 g, 1.18 mmol) were added and this mixture was evacuated and purged with argon several times to remove oxygen from the solution. Copper(I)iodide (45 mg, 0.24 mmol) was added and the reaction mixture was stirred at 70° C. for 5 hrs. The residue was taken up in water, extracted three times with ethyl acetate and several times with water. The combined organic extracts were dried with sodium sulfate, filtered and evaporated. The crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient). The desired product was obtained as a black solid (4.1 g, 79%).

Aufarbeitung

  1. customthis mixture was evacuated
  2. custompurged with argon several times
  3. customto remove oxygen from the solution
  4. extractionextracted three times with ethyl acetate and several times with water
  5. dry with materialThe combined organic extracts were dried with sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient)

Quellen und Nachweise

ORD-Eintrag
ord-7d3bfd896b1a405289e86edc6d6d7c1d
Quelldatensatz
uspto-grants-2010_02
Patentnummer
US07659401B2

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