Réaction #2028875

Équation de réaction

sodium methoxide

Dimethyl oxalate

4′-fluoroacetophenone

hydrochloric acid

→

methyl 4-[4-fluorophenyl]-2,4-diketobutanoate

Solvants

methanol

Conditions de réaction

Traitement

1. 1
   AutreThe reaction flask was placed in a sonication bath
2. 2
   AutreThe reaction was sonicated at 45° C. for 16 hours
3. 3
   workup.ADDITIONA magnetic stirrer was added
4. 4
   TempératureThe suspension was cooled to 0° C.
5. 5
   workup.WAITheld for 30 minutes
6. 6
   FiltrationThe solid was filtered
7. 7
   Lavagethe filter cake was then washed with cold water (100 mL)
8. 8
   AutreUpon drying

Mode opératoire

Dimethyl oxalate (18.80 g, 0.159 mol) and 4′-fluoroacetophenone (20.0 g, 0.145 mol) were charged to a 1000 mL round-bottom flask and diluted with methanol (400 mL). The reaction flask was placed in a sonication bath (Bransonic 1200), and sodium methoxide (25% in methanol, 70 mL) was added over 25 minutes. The reaction was sonicated at 45° C. for 16 hours. The reaction became an insoluble mass during this time. The solid was mechanically broken up, then poured into a hydrochloric acid solution (1N, 500 mL). A magnetic stirrer was added, and the white suspension was stirred vigorously at room temperature for 60 minutes. The suspension was cooled to 0° C. and held for 30 minutes. The solid was filtered, and the filter cake was then washed with cold water (100 mL). Upon drying, methyl 4-[4-fluorophenyl]-2,4-diketobutanoate was obtained (22.91 g, 70.6%) as the enol: 1H NMR (CDCl3/300 MHz) 8.03 (ddd, J=8.86 Hz, J=8.66 Hz, J=5.03 Hz, 2H), 7.19 (dd, J=8.86 Hz, J=8.66 Hz, 2H), 7.04 (s, 1H), 3.95 (s, 3H). 19F NMR (CDCl3/282.2 MHz) −103.9(m).

Source