Sodium bis(trimethylsilyl)amide → 3-(But-3-yn-1-yl)benzonitrile

HRID 1397366Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1397366
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[C:12](Br)=[CH:13][CH2:14][CH2:15][C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[C:19]#[N:20].[Li]CCCC>C1COCC1>[CH2:15]([C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][CH:23]=1)[C:19]#[N:20])[CH2:14][C:13]#[CH:12]

Komponenten

5

Edukt 3

HCID 2724254Sodium bis(trimethylsilyl)amideHCID 866775953-(4,4-Dibromobut-3-en-1-yl)benzonitrileHCID 178418339Butyllithium

Produkt 1

HCID 541923053-(But-3-yn-1-yl)benzonitrileAusbeute 54,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-70 °C

Versuchsvorschrift

Sodium bis(trimethylsilyl)amide (10.7 mL, 10.7 mmol, 1 M in THF) was added dropwise to a solution of 3-(4,4-dibromobut-3-en-1-yl)benzonitrile (2.25 g, 7.14 mmol) in dry THF (45 mL) at −60° C. The reaction mixture was stirred for another 0.5 h maintaining the same temperature. The mixture was then cooled to −70° C. and n-BuLi (8.9 mL, 14.3 mmol, 1.6 M in hexane) was added dropwise. The reaction mixture was stirred for 0.5 h, quenched with saturated NH4Cl solution, and extracted with EtOAc. The combined extracts were concentrated under reduced pressure to obtain the 3-(but-3-yn-1-yl)benzonitrile (600 mg, yield 54%). 1H NMR (300 MHz, CDCl3) δ 7.55 (m, 1H), 7.53-7.51 (m, 1H), 7.48-7.39 (m, 2H), 2.90-2.85 (m, 2H), 2.54-2.48 (td, J=7.2 Hz, 2.6 Hz, 2H), 2.01-1.99 (t, J=2.6 Hz, 1H).

Aufarbeitung

  1. temperaturemaintaining the same temperature
  2. stirringThe reaction mixture was stirred for 0.5 h
  3. customquenched with saturated NH4Cl solution
  4. extractionextracted with EtOAc
  5. concentrationThe combined extracts were concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-41127b54704a41b98d393ef681799325
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08901156B2

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