反応 #2254202

反応方程式

p-fluorophenylmagnesium bromide

Methyl 2-cyano-2-(oxan-4-ylidene)acetate

→

methyl 2-cyano-2-[4-(4-fluorophenyl)oxan-4-yl]acetate

溶媒

diethyl ether

diethyl ether

反応条件

後処理

1. 1
   その他A round bottom flask was equipped with a condenser, addition funnel
2. 2
   温度while cooling the reaction flask in an ice bath
3. 3
   抽出The product was extracted with Et2O (3×50 ml)
4. 4
   洗浄washed with brine (50 ml)
5. 5
   その他dried (NA2SO4)
6. 6
   濃縮concentrated
7. 7
   その他Purified by normal phase SiO2 chromatography (7% to 60% EtOAc/hexanes)

実験手順

A round bottom flask was equipped with a condenser, addition funnel and rubber septum with nitrogen inlet was charged with a solution of p-fluorophenylmagnesium bromide (2.0 M in diethyl ether, 1.99 ml, 3.97 mmol) and CuI (63 mg, 0.331 mmol) in 10 ml dry diethyl ether (10 ml). Methyl 2-cyano-2-(oxan-4-ylidene)acetate (600 mg, 3.31 mmol) in diethyl ether (10 ml) was added drop-wise over 30 min while cooling the reaction flask in an ice bath. The mixture was then stirred for 3 h. The reaction mixture was poured into a 50 g ice/1 N HCl (25 ml) mixture. The product was extracted with Et2O (3×50 ml), washed with brine (50 ml), dried (NA2SO4) and concentrated. Purified by normal phase SiO2 chromatography (7% to 60% EtOAc/hexanes) to give methyl 2-cyano-2-[4-(4-fluorophenyl)oxan-4-yl]acetate as a white solid (730 mg, 80%, m/z: 277.1 [M+Na]+ observed).

出典