Reaktion #365023

Reaktionsgleichung

2-amino-5-bromobenzonitrile

3-chlorophenyl boronic acid

sodium carbonate

→

4-amino-3′-chloro-biphenyl-3-carbonitrile

Ausbeute 87.0%

Lösungsmittel

DME

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigewas degassed
2. 2
   Sonstigeto remove the oxygen
3. 3
   TemperaturThe reaction mixture was cooled to ambient temperature
4. 4
   Sonstigequenched with a saturated aqueous ammonium chloride solution (80 mL)
5. 5
   workup.ADDITIONEthyl acetate (200 mL) was added
6. 6
   Sonstigethe organic layer was separated
7. 7
   Extraktionthe aqueous layer was extracted with ethyl acetate (3×40 mL)
8. 8
   WaschenThe combined organic layers were washed with brine
9. 9
   Trocknendried with MgSO4
10. 10
    SonstigeThe solvent was removed in vacuo
11. 11
    Sonstigethe residue was purified by a silica gel flash chromatography (hexane:ethyl acetate/4:1)

Vorschrift

A mixture of 2-amino-5-bromobenzonitrile (10 g, 50 mmol), 3-chlorophenyl boronic acid (9.5 g, 60 mmol), tetrakis(triphenylphosphine)-palladium(0) (3.5 g, 3 mmol), and sodium carbonate (13 g, 120 mmol) in a mixture of DME and water (100 mL/25 mL) was degassed to remove the oxygen and then heated to 85° C. under a blanket of nitrogen for 5 hours. The reaction mixture was cooled to ambient temperature and quenched with a saturated aqueous ammonium chloride solution (80 mL). Ethyl acetate (200 mL) was added, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (3×40 mL). The combined organic layers were washed with brine and dried with MgSO4. The solvent was removed in vacuo and the residue was purified by a silica gel flash chromatography (hexane:ethyl acetate/4:1) to afford 4-amino-3′-chloro-biphenyl-3-carbonitrile as an off-white solid (8 g, 87%): mp 118-119° C.; 1H-NMR (DMSO-d6) δ 7.80 (d, 1H, J=2.3 Hz), 7.65-7.72 (m, 2H), 7.57 (d, 1H, J=8.0 Hz), 7.42 (t, 1H, J=7.9 Hz), 7.31 (m, 1H), 6.87 (d, 1H, J=8.7 Hz), 6.29 (br, 2H); Anal. Calc. For C13H9ClN2: C, 68.28, H. 3.97, N, 12.25. Found: C, 67.68, H, 4.06, N, 11.89.

Quelle