反应详情

温度

75 °C

A 500 mL three neck round bottom flask with thermowell was fitted with a condenser which vented to a trap and then an aqueous 10% NaOH scrubber, magnetic stir bar, two stoppers and a thermometer. To the vessel was added 4,5,6-trichloropicolinic acid (86 g which contained 8.6 g water, 77.4 g active, 0.32 mol), toluene (160 mL), thionyl chloride (85 mL, 1.12 mol) and DMF (0.3 mL). The slurry was heated to 70-80° C., held there for 7 h and then cooled to room temperature and allowed to stir overnight. Approximately 0.2 mL of the pale yellow solution was placed in a vial and concentrated to a solid under a stream of N2. The solid was treated with a mixture of triethylamine/methanol (0.3 mL/2 mL) and then warmed with a heat gun for ca. 1 min. HPLC analysis indicated that less than 1% of the carboxylic acid remained as compared to the methyl ester derivative. The solution was concentrated on a rotary evaporator leaving a pale yellow solid. The solid was dried (40° C./20 mmHg) for about 1 h providing the title compound (92 g): mp 68-70° C.; 1H NMR (CDCl3, 400 MHz) δ 8.12 (s), the solid contained about 4 wt % toluene as determined by integration of the proton signals; 13C NMR (CDCl3, 101 MHz) δ 167.3, 151.0, 145.82, 145.8, 135.7, 125.5.

1. customvented to a trap
2. temperaturecooled to room temperature
3. concentrationconcentrated to a solid under a stream of N2
4. additionThe solid was treated with a mixture of triethylamine/methanol (0.3 mL/2 mL)
5. temperaturewarmed with a heat gun for ca. 1 min
6. concentrationThe solution was concentrated on a rotary evaporator
7. customleaving a pale yellow solid
8. customThe solid was dried (40° C./20 mmHg) for about 1 h