1-Iodo-3-nitrobenzene → 1-Nitro-3-[2-(trimethylsilyl)ethynyl]-benzene

HRID 1424547Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1424547
I[C:2]1[CH:3]=[C:4]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:6][CH:7]=1.[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13]>CCN(CC)CC.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>[CH3:11][Si:12]([CH3:14])([CH3:13])[C:15]#[C:16][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1

Komponenten

6

Edukt 2

HCID 125741-Iodo-3-nitrobenzeneHCID 66111Trimethylsilylacetylene

Produkt 1

HCID 114700401-Nitro-3-[2-(trimethylsilyl)ethynyl]-benzeneAusbeute 94 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

A mixture of 3-iodonitrobenzene (2.0 g, 8.0 mmol), bis(triphenylphosphine)palladium(II) chloride (0.30 g, 0.40 mmol) and copper(I) iodide (0.080 g, 0.40 mmol) in 25 mL of Et3N was degassed by freeze/pump/thaw technique (three times). Trimethylsilylacetylene (1.0 g, 10 mmol) was added and the mixture was stirred for 12 hours. The reaction mixture was filtered through a celite pad and the pad was rinsed with CH2Cl2. The filtrate was washed with sat. NH4Cl (aq.) and brine and the organic layer was dried (Na2SO4), filtered, and concentrated. The residue was purified by column chromatography (Hexane, then EtOAc;Hexanes =1:30) to afford trimethyl((3-nitrophenyl)ethynyl)silane (1.65 g, 94%): 1H-NMR (300 MHz, CDCl3) δ 8.32 (dd, J=1.8, 1.8 Hz, 1H), 8.17 (ddd, J=8.4, 2.1, 0.9 Hz, 1H), 7.76 (ddd, J=7.5, 1.2, 1.2 Hz, 1H), 7.49 (dd, J=8.1, 8.1 Hz, 1H), 0.28 (s, 9H).

Aufarbeitung

  1. customwas degassed by freeze/pump/thaw technique (three times)
  2. filtrationThe reaction mixture was filtered through a celite pad
  3. washthe pad was rinsed with CH2Cl2
  4. washThe filtrate was washed with sat. NH4Cl (aq.) and brine
  5. dry with materialthe organic layer was dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography (Hexane

Quellen und Nachweise

ORD-Eintrag
ord-1896b23a09c943e197957a5ad6cf9e30
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08927728B2

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