Реакция #2389082

Уравнение реакции

ammonium chloride

water

cyclooctanone

Hydroxylamine-O-sulfonic acid

→

2-Azacyclononanone

Выход 65.0%

Растворители

formic acid

formic acid

Условия реакции

Обработка

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

Методика

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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