Toluene → Acetamide, N-(4-cyano-2-fluorophenyl)-

HRID 2180701

Reaktionsgleichung

Reaktionsgleichung von HRID 2180701
[C-]#N.[Na+].Br[C:5]1[CH:10]=[CH:9][C:8]([NH:11][C:12](=[O:14])[CH3:13])=[C:7]([F:15])[CH:6]=1.C1(C)C=CC=CC=1.[CH3:23][NH:24]CCNC>N.[Cu]I>[C:23]([C:5]1[CH:10]=[CH:9][C:8]([NH:11][C:12](=[O:14])[CH3:13])=[C:7]([F:15])[CH:6]=1)#[N:24]

Komponenten

7

Edukt 4

HCID 1140TolueneHCID 8070N,N'-DimethylethylenediamineHCID 8929Sodium CyanideHCID 67593N-(4-bromo-2-fluorophenyl)acetamide

Produkt 1

HCID 11344323Acetamide, N-(4-cyano-2-fluorophenyl)-Ausbeute 87 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 222AmmoniaLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A Schlenk tube was charged with NaCN (137 mg, 2.80 mmol), CuI (44 mg, 0.23 mmol, 10 mol %), KI (77 mg, 0.46 mmol, 20 mol %), and N-(4-bromo-2-fluorophenyl)acetamide (540 mg, 2.33 mmol), briefly evacuated and backfilled with argon three times. Anhydrous toluene (1.2 mL) and N,N′-dimethylethylenediamine (250 μL, 2.35 mmol) were added under argon. The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred at 110° C. for 24 h. The resulting suspension was allowed to reach room temperature, diluted with 30% aq ammonia (2 mL), and extracted with ethyl acetate (4×2 mL). The combined organic phases were dried over MgSO4, concentrated, and the residue was purified by flash chromatography on silica gel (hexane/ethyl acetate 1:1) to provide the desired product as a fine white powder (337 mg, 87% yield). Mp 169.5-171.5° C.; 1H NMR (400 MHz, CDCl3, J values are reported in Hz): δ 8.59 (t, J=8.4, 1H), 7.63 (bs, 1H), 7.48 (d, J=8.4, 1H), 7.41 (dd, J=10.6, J=1.8, 1H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3): 169.0, 151.3 (d, J=244 Hz), 131.6 (d, J=9.6 Hz), 129.9 (d, J=3.5 Hz), 121.9, 118.7 (d, J=22.8 Hz), 118.1 (d, J=2.9 Hz), 107.1 (d, J=9.3 Hz), 25.3; IR (neat, cm−1): 3317, 2235, 1699, 1593, 1515, 834, 707. Anal. Calcd. for C9H7FN2O: C, 60.67; H, 3.96; N, 15.72. Found: C, 60.42; H, 3.94; N, 15.63.

Aufarbeitung

  1. custombriefly evacuated
  2. customThe Schlenk tube was sealed with a Teflon valve
  3. customto reach room temperature
  4. extractionextracted with ethyl acetate (4×2 mL)
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. concentrationconcentrated
  7. customthe residue was purified by flash chromatography on silica gel (hexane/ethyl acetate 1:1)

Quellen und Nachweise

ORD-Eintrag
ord-c942e8199ed54f9a83f463f2b424b51e
Quelldatensatz
uspto-grants-2005_05
Patentnummer
US06888032B2

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