Ammonium Chloride → HCID 86709177, Verbindung

HRID 1851121Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1851121
[Cl:1][C:2]1[C:9](I)=[C:8]([F:11])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[C:12]([Si:14]([CH3:17])([CH3:16])[CH3:15])#[CH:13].[NH4+].[Cl-]>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.C1COCC1>[Cl:1][C:2]1[C:9]([C:13]#[C:12][Si:14]([CH3:17])([CH3:16])[CH3:15])=[C:8]([F:11])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5]

Komponenten

7

Edukt 3

HCID 25517Ammonium ChlorideHCID 66111TrimethylsilylacetyleneHCID 690587802-Chloro-4-fluoro-3-iodobenzonitrile

Produkt 1

HCID 86709177HCID 86709177, VerbindungAusbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A thick-walled glass pressure vessel was charged with 2-chloro-4-fluoro-3-iodobenzonitrile (2.815 g, 10.00 mmol), Pd(PPh3)2Cl2 (0.351 g, 0.500 mmol), and CuI (0.095 g, 0.500 mmol) and sealed with a rubber septum. Anhydrous THF (25 mL) and DIPA (4.22 mL, 30.0 mmol) were added via syringe and the mixture was degassed 10 min by sparging with N2 while immersed in an ultrasonic cleaning bath. To the degassed mixture was added ethynyltrimethylsilane (4.24 mL, 30.0 mmol), the vessel was resealed with a PTFE bushing, and the mixture was stirred in a heating block at 50° C. After 41 h, the mixture was cooled and poured into half-satd NH4Cl. The whole was filtered through a pad of Celite and the filtrate was extracted with EtOAc (×3). Combined organics were washed (water, brine), dried over Na2SO4 and concentrated in vacuo. The residue was purified by low pressure liquid chromatography (silica gel, EtOAc/hexanes, gradient elution) affording 2-chloro-4-fluoro-3-((trimethylsilyl)ethynyl)benzonitrile (2.29 g, 91% yield) as a pale yellow solid: 1H NMR (400 MHz, CDCl3) δ 7.60 (dd, J=8.7, 5.4 Hz, 1H), 7.12 (dd, J=8.7, 7.9 Hz, 1H), 0.30 (s, 9H); MS (GCMS EI) m/z 251 ([M]+, 14%), 236 ([M-CH3]+, 100%).

Aufarbeitung

  1. customsealed with a rubber septum
  2. customthe mixture was degassed 10 min
  3. customby sparging with N2
  4. customwhile immersed in an ultrasonic cleaning bath
  5. temperaturethe mixture was cooled
  6. filtrationThe whole was filtered through a pad of Celite
  7. extractionthe filtrate was extracted with EtOAc (×3)
  8. washCombined organics were washed (water, brine)
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by low pressure liquid chromatography (silica gel, EtOAc/hexanes, gradient elution)

Quellen und Nachweise

ORD-Eintrag
ord-57dddc3834fe4df0958709259c4a0c9e
Quelldatensatz
uspto-grants-2015_02
Patentnummer
US08957104B2

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