Trimethylsilylacetylene → 4-Amino-2-chloro-5-[(trimethylsilyl)ethynyl]benzonitrile

HRID 475271Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 475271
[NH2:1][C:2]1[C:9](I)=[CH:8][C:5]([C:6]#[N:7])=[C:4]([Cl:11])[CH:3]=1.CCN(C(C)C)C(C)C.[C:21]([Si:23]([CH3:26])([CH3:25])[CH3:24])#[CH:22]>[Cu]I>[NH2:1][C:2]1[C:9]([C:22]#[C:21][Si:23]([CH3:26])([CH3:25])[CH3:24])=[CH:8][C:5]([C:6]#[N:7])=[C:4]([Cl:11])[CH:3]=1

Komponenten

5

Edukt 3

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 109128704-amino-2-chloro-5-iodobenzonitrile

Produkt 1

HCID 862227914-Amino-2-chloro-5-[(trimethylsilyl)ethynyl]benzonitrileAusbeute 48,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Katalysator

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

A round bottom bottle was charged with 236 (2.78 g, 0.01 mol), CuI (95 mg, 0.5 mmol), Pd(PPh3)Cl2 (200 mg, 0.5 mmol), DIPEA (3.87 g, 0.03 mol) and ethynyltrimethylsilane (2.94 g, 0.03 mol). The mixture was heated under nitrogen atmosphere at 70° C. overnight then cooled and partitioned between EtOAc (500 mL) and H2O (100 mL). The organic layer was concentrated to dryness in vacuo. The crude was purified by SiO2 chromatography eluting with 10% EtOAc/petroleum ether to afford 1.2 g (48%) of 4-amino-2-chloro-5-((trimethylsilyl)ethynyl)benzonitrile (238) as brown solid: MS (ESI) m/z=249.1 [M+1]+

Aufarbeitung

  1. temperaturethen cooled
  2. custompartitioned between EtOAc (500 mL) and H2O (100 mL)
  3. concentrationThe organic layer was concentrated to dryness in vacuo
  4. customThe crude was purified by SiO2 chromatography
  5. washeluting with 10% EtOAc/petroleum ether

Quellen und Nachweise

ORD-Eintrag
ord-2f72a036910d4624a235a422db855eee
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08637537B2

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