反应详情

温度

70 °C

Into a solution of 5 g of water and 15.3 g (150 mmol) of concentrated hydrochloric acid is added dropwise 4.60 g (50 mmol) of aniline. The temperature of the reaction mixture during the addition step is kept under 40° C. After the addition is complete, the reaction mixture is heated to 70° C. for one hour. The reaction mixture is then cooled to 0° to 5° C. followed by a dropwise addition of an aqueous solution of 3.45 g (50 mmol) of sodium nitrite in 10 mL of water. The addition time is 20 minutes while the reaction temperature is maintained at 0° to 5° C. The reaction mixture is transferred to a cold-jacketed addition funnel and is then added dropwise into a solution of 3.9 g (25 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine, 25 mg (0.25 mmol) of copper(II) fluoride in 120 mL of pyridine at 70° C. Evolution of nitrogen is observed during the addition. After the addition is complete, the reaction mixture is kept at 70° C. for another 30 minutes followed by cooling to ambient temperature. The reaction mixture is concentrated to a thick oil. The crude product is purified by vacuum flash chromatography (heptane) to give 3.97 g of the title as a colorless oil in 68.4% yield.

1. additionThe temperature of the reaction mixture during the addition step
2. customis kept under 40° C
3. additionAfter the addition
4. temperatureThe reaction mixture is then cooled to 0° to 5° C.
5. temperatureis maintained at 0° to 5° C
6. customThe reaction mixture is transferred to a cold-jacketed addition funnel
7. additionEvolution of nitrogen is observed during the addition
8. additionAfter the addition
9. waitthe reaction mixture is kept at 70° C. for another 30 minutes
10. temperatureby cooling to ambient temperature
11. concentrationThe reaction mixture is concentrated to a thick oil
12. customThe crude product is purified by vacuum flash chromatography (heptane)
13. customto give 3.97 g of the title as a colorless oil in 68.4% yield