反応 #1830

反応方程式

2,3,4,5-tetrahydro-1H-1-benzazepin-2-one

sodium sulfite

sodium sulfite

hexamethyldisilazane

iodine

→

product

収率 57.5%

3-Iodo-2,3,4,5-tetrahydro-1H-1-benzazepin-2-one

収率 57.5%

溶媒

water

methylene chloride

反応条件

後処理

1. 1
   温度was heated
2. 2
   温度at reflux for 10 minutes
3. 3
   温度The mixture was heated
4. 4
   温度at reflux for 2.5 hours
5. 5
   温度then cooled to room temperature
6. 6
   workup.ADDITIONwas poured the reaction mixture in several portions
7. 7
   温度while maintaining the temperature below 10° C
8. 8
   洗浄The reaction vessel was rinsed with 22.33 L of methylene chloride
9. 9
   workup.STIRRINGThe quenching mixture was stirred vigorously
10. 10
    その他to separate
11. 11
    その他The aqueous layer was removed
12. 12
    洗浄The combined organic layers were washed with 11 L of water
13. 13
    濃縮concentrated under vacuum to a final volume of approximately 5 L
14. 14
    workup.ADDITIONThe residue was treated with 55 L of toluene
15. 15
    濃縮concentrated under vacuum to a final volume of 10 L
16. 16
    その他The resulting slurry was removed by filtration
17. 17
    洗浄the filter cake washed with an additional 5 L of toluene
18. 18
    その他dried under vacuum at ambient temperature for 24 hours

実験手順

A suspension of 1.8 Kg (11.17 mol) of 2,3,4,5-tetrahydro-1H-1-benzazepin-2-one in a mixture of 22.33 L of methylene chloride and 11.78 L (55.83 mol) of hexamethyldisilazane was heated at reflux for 10 minutes then cooled to 30° C. and treated with 8.503 Kg (33.5 mol) of iodine in one portion. The mixture was heated at reflux for 2.5 hours then cooled to room temperature. Aqueous sodium sulfite containing 4.926 Kg of sodium sulfite in 44 L of water was cooled to 0° C. and into it was poured the reaction mixture in several portions with vigorous stirring while maintaining the temperature below 10° C. The reaction vessel was rinsed with 22.33 L of methylene chloride and the washing transferred to the quenching mixture. The quenching mixture was stirred vigorously and the layers allowed to separate. The aqueous layer was removed and reextracted with 22.33 L of methylene chloride. The combined organic layers were washed with 11 L of water and concentrated under vacuum to a final volume of approximately 5 L. The residue was treated with 55 L of toluene and concentrated under vacuum to a final volume of 10 L. The resulting slurry was removed by filtration and the filter cake washed with an additional 5 L of toluene and dried under vacuum at ambient temperature for 24 hours to give 1.842 Kg (6.42 mol, 57%) of product. 1H NMR (200 MHz,CDCl3): 2.6-2.8 (m,3H), 2.93 (m,1H), 4.64 (t,8 Hz,1H), 6.97 (d,8 Hz,1H), 7.10-7.35 (m,3H), 7.55 (br s,1H).

出典