反応 #2389082

反応方程式

ammonium chloride

water

cyclooctanone

Hydroxylamine-O-sulfonic acid

→

2-Azacyclononanone

収率 65.0%

溶媒

formic acid

formic acid

反応条件

後処理

1. 1
   その他A 5 L three-neck round bottom flask was fitted with a heating mantle, an overhead mechanical stirrer, an addition funnel
2. 2
   その他to form a white slurry
3. 3
   workup.ADDITIONAfter the addition
4. 4
   その他the addition funnel was replaced by a reflux condenser
5. 5
   温度the reaction was heated
6. 6
   その他to give a brown solution
7. 7
   温度After the solution was cooled to room temperature
8. 8
   抽出The aqueous mixture was extracted with chloroform (3×1200 mL)
9. 9
   workup.ADDITIONwas added slowly
10. 10
    その他The chloroform layer was then separated
11. 11
    乾燥dried over anhydrous sodium sulfate
12. 12
    その他evaporated under reduced pressure
13. 13
    その他to afford a
14. 14
    その他The oil Was placed in a 5.00 mL round bottom flask with a magnetic stirrer
15. 15
    その他The round bottom flask was placed in a silicon oil bath
16. 16
    その他was fitted with a short path vacuum distillation head
17. 17
    その他equipped with a thermometer

実験手順

A 5 L three-neck round bottom flask was fitted with a heating mantle, an overhead mechanical stirrer, an addition funnel, and a thermometer. The reaction was performed under an argon atmosphere. Hydroxylamine-O-sulfonic acid (196.7 g, 1.74 moles, 1.10 equiv.) and formic acid (1 L) were charged into the round bottom flask and stirred to form a white slurry. A solution of cyclooctanone (200.0 g 1.58 moles, 1.0 equiv.) in formic acid (600 mL) was added dropwise to the white slurry via the addition funnel. After the addition, the addition funnel was replaced by a reflux condenser, and the reaction was heated to reflux (internal temperature about 105° C.) for 1 hour to give a brown solution. After the solution was cooled to room temperature, it was poured into a mixture of saturated aqueous ammonium chloride (1.5 L) and water (1.5 L). The aqueous mixture was extracted with chloroform (3×1200 mL). The combined chloroform layers were transferred into a breaker, and saturated sodium bicarbonate (2 L) was added slowly. The chloroform layer was then separated, dried over anhydrous sodium sulfate, and evaporated under reduced pressure to afford a. brown oil. The oil Was placed in a 5.00 mL round bottom flask with a magnetic stirrer. The round bottom flask was placed in a silicon oil bath and was fitted with a short path vacuum distillation head equipped with a thermometer. A Cow-type receiver was connected to three 250 mL flasks. 2-Azacyclononanone (145 g, 65%, mp 64-69° C.) was obtained by vacuum distillation (fraction with head temperature range from 80 to 120° C. at pressures between 3.0 and 3.4 mmHg).

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