反応 #581039

反応方程式

HCl

2-amino-4-chlorobenzonitrile

Et2O

MeMgCl

HCl

→

title material

1-(2-amino-4-chlorophenyl)ethanone

反応条件

後処理

1. 1
   workup.STIRRINGStirring
2. 2
   その他was removed
3. 3
   workup.STIRRINGthe reaction stirred for 21 h at rt
4. 4
   温度to warm slowly to rt within the cooling bath
5. 5
   その他The Et2O layer was separated
6. 6
   workup.ADDITIONby addition of solid KOH
7. 7
   抽出later extracted with EtOAc (3×)
8. 8
   乾燥dried (Na2SO4)
9. 9
   濃縮concentrated under reduced pressure

実験手順

To a vigourosly stirred, Et2O (100 mL) solution of 2-amino-4-chlorobenzonitrile (1.00 g, 6.55 mmol) cooled in an ice-H2O bath was added MeMgCl (3.0 M in THF, 6.5 mL, 19.7 mmol) dropwise over 5 min. During that time the reaction became a thick yellow suspension. Stirring was continued at the temperature for 1 h before the cooling bath was removed and the reaction stirred for 21 h at rt. The resultant light yellow suspension cooled to −60° C. and treated with aq HCl (5 M, 8 mL, 40 mmol) dropwise over 3 min. The mixture was allowed to warm slowly to rt within the cooling bath. Later more aq HCl (5 M, 6.5 mL, 33 mmol) was added. The Et2O layer was separated, the aq phase was basicified (pH 4-5) by addition of solid KOH and later extracted with EtOAc (3×). The Et2O and EtOAc layers were combined, dried (Na2SO4) and concentrated under reduced pressure to afford the title material which was used without further purification; 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J=8.4 Hz, 1H), 6.65 (d, J=2.0 Hz, 1H), 6.60 (dd, J=2.0 Hz, 8.0 Hz, 1H), 6.40 (br, 2H), 2.55 (s, 3H); MS (ES+): m/z 170.07 (100) [MH+]; HPLC: tR=3.12 min (OpenLynx, polar—5 min).

出典