反応 #1106608

反応方程式

N,N-diethylaniline hydrochloride

1,2-bis(trifluoroacetyl)hydrazine

phosphoryl chloride

→

2,5-dichloro-1,1,1,6,6,6-hexafluoro-3,4-diazahexa-2,4-diene

収率 53.0%

反応条件

後処理

1. 1
   その他fitted with a condenser
2. 2
   その他leading to a cold trap
3. 3
   その他(−78° C.)
4. 4
   温度The mixture was heated
5. 5
   温度under reflux for 5 h
6. 6
   温度to cool
7. 7
   workup.WAITstored overnight
8. 8
   その他condensed in the cold trap
9. 9
   その他the two layers which had formed
10. 10
    その他were separated
11. 11
    workup.ADDITIONThe layer was added to ice water (85 mL)
12. 12
    workup.STIRRINGthe mixture vigorously stirred for 1 h in a flask
13. 13
    その他fitted with a condenser
14. 14
    その他Separation of the lower organic layer
15. 15
    その他gave the main batch of the crude product (6.4 g)
16. 16
    その他the organic layer subjected to preliminary purification by trap-to-trap
17. 17
    workup.DISTILLATIONdistillation in vacuum
18. 18
    その他to afford a second batch of crude product (1.6 g)
19. 19
    workup.DISTILLATIONDistillation of the combined product through a vacuum-jacketed Vigreux column

実験手順

A mixture of N,N-diethylaniline hydrochloride (18.5 g, 0.1 mol), 1,2-bis(trifluoroacetyl)hydrazine (10.3 g, 0.46 mol) and phosphoryl chloride (160 mL) was stirred for 30 minutes under nitrogen in a flask fitted with a condenser leading to a cold trap (−78° C.). The mixture was heated under reflux for 5 h and then allowed to cool and stored overnight. The flask contents and the small amount of material which had condensed in the cold trap were combined and the two layers which had formed were separated. The layer was added to ice water (85 mL) and the mixture vigorously stirred for 1 h in a flask fitted with a condenser. Separation of the lower organic layer gave the main batch of the crude product (6.4 g). The original dark upper layer was treated similarly with ice water (75 mL) and the organic layer subjected to preliminary purification by trap-to-trap distillation in vacuum to afford a second batch of crude product (1.6 g). Distillation of the combined product through a vacuum-jacketed Vigreux column gave 2,5-dichloro-1,1,1,6,6,6-hexafluoro-3,4-diazahexa-2,4-diene (6.3 g, 53%) as an oil.

出典