Water → 3-(Trimethylsilylethynyl)pyridine

HRID 2362350

Reaktionsgleichung

Reaktionsgleichung von HRID 2362350
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C(N(CC)CC)C.[C:15]([Si:17]([CH3:20])([CH3:19])[CH3:18])#[CH:16].O>C(OCC)(=O)C.[Cu]I.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>[CH3:18][Si:17]([C:15]#[C:16][C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1)([CH3:20])[CH3:19]

Komponenten

8

Edukt 4

HCID 962WaterHCID 8471TriethylamineHCID 122863-BromopyridineHCID 66111Trimethylsilylacetylene

Produkt 1

HCID 41008573-(Trimethylsilylethynyl)pyridine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A flask was charged with 3-bromopyridine (1.22 mL, 12.66 mmol) and triethylamine (40 mL) and sparged with nitrogen for 15 min. To this was added ethynyltrimethylsilane (1.97 mL, 13.92 mmol) and the reaction purged 15 min longer. To this was added copper(I) iodide (0.121 g, 0.633 mmol), and Pd(PPh3)2Cl2 (0.444 g, 0.633 mmol). The reaction was stirred at room temperature for 72 h. The reaction was diluted with ethyl acetate (60 mL) and poured into water. The black heterogeneous emulsion was filtered through a plug of celite and the layers separated. The organics were washed with brine, dried over magnesium sulfate, and concentrated. Column chromatography (5%-->15% EtOAc/Hex) gave 1.70 g (77%) as a dark oil. 1H-NMR (CDCl3, 500 MHz) δ 8.71 (m, 1H), 8.55 (dd, J=4.9, 1.5, 1H), 7.76 (ddd, J=7.9, 1.8, 1.8, 1H), 7.26 (ddd, J=7.9, 4.9, 0.6, 1H), 0.29 (s, 9H). 13C-NMR (CDCl3, 126 MHz) δ 152.8, 148.8, 138.9, 123.0, 120.4, 101.6, 98.3, −0.1. Mass spec.: 176.14 (MH)+.

Aufarbeitung

  1. customsparged with nitrogen for 15 min
  2. customthe reaction purged 15 min longer
  3. filtrationThe black heterogeneous emulsion was filtered through a plug of celite
  4. customthe layers separated
  5. washThe organics were washed with brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated
  8. customColumn chromatography (5%-->15% EtOAc/Hex) gave 1.70 g (77%) as a dark oil

Quellen und Nachweise

ORD-Eintrag
ord-c3bbe896a5504bda80c5ea93decad170
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08691821B2

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