反応 #4173

反応方程式

N-[5-bromo-2-(2,3-dihydro-1H-indol-1-yl)phenyl]-N',N'-dimethylurea

→

product

収率 48.0%

9-Bromo-6-dimethylamino-1,2-dihydrobenzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepine

収率 48.0%

溶媒

phosphorus oxychloride

反応条件

後処理

1. 1
   温度under nitrogen, was heated
2. 2
   温度under reflux for 6 hours
3. 3
   その他The excess phosphorus oxychloride was removed under vacuum with gentle warming
4. 4
   温度The residue was chilled in an ice-bath (with exclusion of moisture)
5. 5
   workup.ADDITIONtreated first with 250 ml of ice-cold 2N sodium hydroxide solution
6. 6
   workup.STIRRINGThe mixture was stirred
7. 7
   その他triturated until all the material
8. 8
   その他The organic phase was separated
9. 9
   洗浄washed with 2N sodium hydroxide solution, twice with water
10. 10
    乾燥dried over anhydrous sodium sulfate
11. 11
    ろ過filtered
12. 12
    濃縮concentrated in vacuo to an oil
13. 13
    workup.DISSOLUTIONThe oil was dissolved in 50 ml of ethyl acetate
14. 14
    濃縮the solution was concentrated under a stream of nitrogen
15. 15
    ろ過At a volume of about 30 ml, the mixture was filtered
16. 16
    その他Concentration of the filtrate was continued to a volume of about 20 ml, during which crystallization
17. 17
    その他resulted
18. 18
    workup.DISSOLUTIONThe solid was dissolved
19. 19
    温度by heating
20. 20
    ろ過the hot solution was filtered
21. 21
    その他to crystallize

実験手順

A mixture of 10.8 g (0.030 mole) of N-[5-bromo-2-(2,3-dihydro-1H-indol-1-yl)phenyl]-N',N'-dimethylurea and 110 ml of phosphorus oxychloride, under nitrogen, was heated under reflux for 6 hours, with stirring, and then cooled to room temperature. The excess phosphorus oxychloride was removed under vacuum with gentle warming. The residue was chilled in an ice-bath (with exclusion of moisture) and treated first with 250 ml of ice-cold 2N sodium hydroxide solution, and then with 500 ml of dichloromethane. The mixture was stirred and triturated until all the material passed into solution. The organic phase was separated, washed with 2N sodium hydroxide solution, twice with water, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to an oil. The oil was dissolved in 50 ml of ethyl acetate and the solution was concentrated under a stream of nitrogen. At a volume of about 30 ml, the mixture was filtered. Concentration of the filtrate was continued to a volume of about 20 ml, during which crystallization resulted. The solid was dissolved by heating, the hot solution was filtered and allowed to crystallize to afford 4.9 g (48%) of product, mp 124°-127° C.

出典