反応 #1824303

反応方程式

sulfuric acid

sodium acetate

acetaldoxime

sodium acetate

N2

3-(trifluoromethyl)aniline

sodium nitrite

→

solid

収率 84.3%

1-[3-(trifluoromethyl)phenyl]ethanone oxime

収率 84.3%

溶媒

water

toluene

water

反応条件

後処理

1. 1
   その他To a three-neck indented, Morton style flask equipped with a sidearm for thermometer
2. 2
   温度cooled to -5° C.
3. 3
   その他to give a slurry
4. 4
   workup.ADDITIONThe rate of addition
5. 5
   温度was maintained between -5 and 0° C
6. 6
   workup.STIRRINGThe mixture was stirred at that temperature for 30 min
7. 7
   workup.ADDITIONwas added
8. 8
   温度cooled to about 10° C
9. 9
   その他a two phase mixture (dark green oil and aqueous) was obtained
10. 10
    workup.STIRRINGThe mixture was stirred for 30 min before the reaction
11. 11
    その他the organic phase separated from the aqueous
12. 12
    抽出The aqueous phase was extracted with another 100 mL of toluene
13. 13
    洗浄were washed with 15% ammonium hydroxide solution (5×20 mL)
14. 14
    洗浄wash
15. 15
    洗浄The organic phase (orange color) was washed with 20 mL of brine
16. 16
    乾燥dried over magnesium sulfate
17. 17
    その他Removal of volatiles on the rotovap
18. 18
    その他gave an orange oil which
19. 19
    その他upon fuirther drying on the vacuum pump

実験手順

To a three-neck indented, Morton style flask equipped with a sidearm for thermometer charged with 80 mL (240 mmol) of 3N sulfuric acid was added 10 mL (80 mmol) of 3-(trifluoromethyl)aniline (Aldrich Chemical Co.). The resulting suspension turned into a clear solution upon heating to 65° C. The solution was stirred vigorously and cooled to -5° C. using an acetone/ice bath to give a slurry. To the slurry was added a solution of 5.85 g (84.8 mmol) of sodium nitrite in 25 mL of water. The rate of addition was carefully adjusted so the internal reaction temperature was maintained between -5 and 0° C. The mixture was stirred at that temperature for 30 min. The diazonium thus obtained appears as a thin slurry. The slurry thickened when a solution of 20 g (244 mmol) of sodium acetate in 50 mL of water was added. Meanwhile, in another flask, 19 mL (320 mmol) of acetaldoxime, 1.50 g (8 mmol) of copper (II) acetate, 0.5 g (4 mmol) of sodium sulfite, and 20 g (244 mmol) of sodium acetate were combined and cooled to about 10° C. To this solution was added via a cannula or additional funnel the diazonium mixture. Immediate gas (N2) evolution was observed, and a two phase mixture (dark green oil and aqueous) was obtained. The mixture was stirred for 30 min before the reaction was worked up. To the mixture was added about 300 mL of toluene and the organic phase separated from the aqueous. The aqueous phase was extracted with another 100 mL of toluene. The combined toluene extracts (greenish color) were washed with 15% ammonium hydroxide solution (5×20 mL). Analysis using copper test strips from EM Science indicated the copper (I/II) content to be less than 10 ppm as compared to greater than 100 ppm before the ammonium hydroxide wash. The organic phase (orange color) was washed with 20 mL of brine and dried over magnesium sulfate. Removal of volatiles on the rotovap gave an orange oil which turned into a semi-solid upon fuirther drying on the vacuum pump to give 13.7 g (84%) of a solid product. In the analytical assay, it was found to contain 58.9% of the desired oxime product.

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