反应详情

温度

128 °C

To a solution of 1-(2-fluorophenyl)-2-(1,1,1-trifluorobut-3-en-2-yloxy)ethanone oxime (1.085 kg, 3.328 mol) in xylenes (6.9 L) was added hydroquinone (86.2 g, 0.8 mol) at rt. The solution was heated to 128° C. (internal temperature) for 18 h. The solution was cooled to rt, and hexanes (7.0 L) was added, followed by 4.0 M aq. HCl (2.4 L). The reaction mixture was stirred for 1 h, and filtered. To the solid was added water (2.0 L), methyl tert-butyl ether (7.0 L) and 25% wt. aq. NaOH (0.4 L). The aq. layer was extracted once with methyl tert-butyl ether (7.0 L), the organics were combined, washed with 27% aq. NaCl (2.0 L) and concentrated under vacuum to a black oil (512.0 g, 56%). 1H NMR (500 MHz, CDCl3) δ ppm 7.64-7.52 (m, 1H), 7.39-7.31 (m, 1H), 7.19 (td, J=7.7, 1.2 Hz, 1H), 7.11 (ddd, J=11.9, 8.2, 1.0 Hz, 1H), 4.54 (d, J=10.1 Hz, 1H), 4.34-4.23 (m, 1H), 4.26-4.17 (m, 1H), 4.16 (d, J=10.2 Hz, 1H), 4.10 (d, J=8.5 Hz, 1H), 3.71 (d, J=20.2 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ ppm 160.59 (d, JCF=247.0 Hz), 130.50 (d, JCF=8.7 Hz), 128.72, 124.69 (d, JCF=3.3 Hz), 124.45 (q, JCF=281.8 Hz), 124.43 (d, JCF=11.9 Hz), 116.66 (d, JCF=22.7 Hz), 83.70 (q, JcF=32.1 Hz), 78.17 (d, JCF=3.1 Hz), 77.63. 54.53.

1. temperatureThe solution was cooled to rt
2. filtrationfiltered
3. additionTo the solid was added water (2.0 L), methyl tert-butyl ether (7.0 L) and 25% wt. aq. NaOH (0.4 L)
4. extractionThe aq. layer was extracted once with methyl tert-butyl ether (7.0 L)
5. washwashed with 27% aq. NaCl (2.0 L)
6. concentrationconcentrated under vacuum to a black oil (512.0 g, 56%)