反応 #1994297

反応方程式

(E)-4-(4-chloro-2-fluorophenyl)-but-3-en-2-one

diethyl oxalate

Sodium

ethyl alcohol

sodium

→

(E)-6-(4-chloro-2-fluoro-phenyl)-2,4-dioxo-hex-5-enoic acid ethyl ester

収率 86.5%

(E)-6-(4-chloro-2-fluorophenyl)-2,4-dioxo-hex-5-enoic acid ethyl ester

収率 86.5%

溶媒

ether

反応条件

後処理

1. 1
   その他the solvent was removed under reduced pressure, and anhydrous ether (200 mL)
2. 2
   workup.ADDITIONwas added
3. 3
   ろ過the yellow solid was filtered
4. 4
   洗浄washed with ether
5. 5
   その他After 1 hour (h) of drying at room temperature
6. 6
   その他the solid was partitioned between CH2Cl2 (200 mL) and 1 N sulfuric acid (H2SO4, 150 mL)
7. 7
   乾燥The organic layer was dried (MgSO4)
8. 8
   その他the solvent was removed

実験手順

Sodium pellets (2.88 g, 0.125 mol) were slowly added to absolute ethyl alcohol (EtOH, 125 mL). After the sodium had reacted, the solvent was removed under reduced pressure, and anhydrous ether (200 mL) was added. The reaction mixture was cooled to −5° C., and a solution of (E)-4-(4-chloro-2-fluorophenyl)-but-3-en-2-one (1; 24.75 g, 0.125 mol) and diethyl oxalate (21.9 g, 0.15 mol) in anhydrous ether (25 mL) was added over 30 min. After stirring 2 days (d) at room temperature, the yellow solid was filtered and washed with ether. After 1 hour (h) of drying at room temperature, the solid was partitioned between CH2Cl2 (200 mL) and 1 N sulfuric acid (H2SO4, 150 mL). The organic layer was dried (MgSO4), and the solvent was removed to give (E)-6-(4-chloro-2-fluoro-phenyl)-2,4-dioxo-hex-5-enoic acid ethyl ester (3; 32.3 g, 86%) as a yellow solid. A small sample was recrystallized from EtOH to yield yellow crystals: mp 84-85° C.; 1H NMR (400 MHz, CDCl3) δ 14.72 (s, 1H), 7.76 (d, J=16.1 Hz, 1H), 7.49 (d, J=8.3 Hz, 1H), 7.24-7.12 (m, 2H), 6.73 (d, J=16.1 Hz, 1H), 6.53 (s, 1H), 4.38 (q, J=7.1 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H); HRMS-ESI (m/z): calcd for C14H12ClFO44, 298.041. found, 298.041.

出典