Trimethylsilylacetylene → Methyl 4-ethynylbenzoate

HRID 527750

Reaktionsgleichung

Reaktionsgleichung von HRID 527750
I[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.C[Si]([C:16]#[CH:17])(C)C>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:16]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1)#[CH:17]

Komponenten

6

Edukt 2

HCID 66111TrimethylsilylacetyleneHCID 69273Methyl 4-iodobenzoate

Produkt 1

HCID 640163Methyl 4-ethynylbenzoateAusbeute 147,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a solution of methyl 4-iodobenzoate (1.5 g, 5.72 mmol) and trimethylsilylacetylene (Aldrich, 1.58 mL, 11.45 mmol) in toluene (12 mL) were added Pd(PPh3)4 (0.66 g, 0.57 mmol), CuI (0.16 g, 0.86 mmol), and TEA (6.4 mL, 45.80 mmol). The resulting reaction mixture was purged with nitrogen for 3 min and stirred at rt for 3 h. The reaction mixture was diluted with ethyl acetate and NH4Cl solution. The organic layer was separated, washed with brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash column chromatography (eluting with 10% EtOAc/hexane) to afford the title compound as a white solid (1.35 g, 96%). 1H NMR (CDCl3) δ 7.98 (d, J=8.6 Hz, 2H), 7.53 (d, J=8.6 Hz, 2H), 3.92 (s, 3H), 0.27 (s, 9H); MS(ESI+) m/z 233.1 (M+H)+.

Aufarbeitung

  1. customThe resulting reaction mixture
  2. customwas purged with nitrogen for 3 min
  3. additionThe reaction mixture was diluted with ethyl acetate and NH4Cl solution
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by flash column chromatography (eluting with 10% EtOAc/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-fd6cd99dcff044b0b717c51cc4dd5ec7
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09345740B2

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