反应详情

温度

0 °C

1H-1,2,4-Triazole (15.1 g, 219 mmol) in acetonitrile (220 mL) was cooled to 0° C. and treated slowly with phosphorus oxychloride (5.99 mL, 65.4 mmol). After 10 minutes, triethylamine (36.5 mL, 262 mmol) was slowly added; the reaction was stirred for an additional 10 minutes at 0° C., then slowly warmed to room temperature over 15 minutes. C5 (5.33 g, 21.8 mmol) was added to the reaction mixture and stirring was continued at room temperature for 2 hours. After concentration in vacuo, the residue was diluted with ethyl acetate (˜250 mL) and poured into ice-cold stirring aqueous potassium phosphate solution (25%, 250 mL). After stirring for 10 minutes, the layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification via silica gel chromatography (small plug of silica gel employed; Eluent: 2:1 heptane/ethyl acetate) provided the product as a bright yellow solid. Yield: 6.50 g, 21.8 mmol, 100%. LCMS m/z 296.0 [M+H]+. 1H NMR (500 MHz, CDCl3) δ 9.06 (s, 1H), 8.35 (s, 1H), 7.77 (s, 1H), 7.74 (ddd, J=7.6, 7.4, 1.8 Hz, 1H), 7.35-7.40 (m, 1H), 7.26 (ddd, J=7.6, 7.5, 1.2 Hz, 1H), 6.88 (ddd, J=10.2, 8.3, 1.1 Hz, 1H), 2.87 (s, 3H).

1. temperatureslowly warmed to room temperature over 15 minutes
2. stirringstirring
3. waitwas continued at room temperature for 2 hours
4. concentrationAfter concentration in vacuo
5. additionthe residue was diluted with ethyl acetate (˜250 mL)
6. additionpoured into ice-cold stirring aqueous potassium phosphate solution (25%, 250 mL)
7. stirringAfter stirring for 10 minutes
8. customthe layers were separated
9. extractionthe aqueous layer was extracted with ethyl acetate
10. dry with materialThe combined organic layers were dried over magnesium sulfate
11. filtrationfiltered
12. concentrationconcentrated under reduced pressure
13. customPurification via silica gel chromatography (small plug of silica gel employed; Eluent: 2:1 heptane/ethyl acetate)