反応 #45310

反応方程式

[2-(aminomethyl)4-(trifluoromethyl)phenyl]amine

N-methylmorpholine

3,5-bis(trifluoromethyl)benzyl bromide

acetic acid

→

[2-amino-5-(trifluoromethyl)benzyl][3,5-bis(trifluoromethyl)benzyl]amine

収率 24.0%

溶媒

dimethoxyethane

ether

hexane

反応条件

後処理

1. 1
   その他In a 500-mL flask equipped with a septum inlet, magnetic stirring bar, and condenser
2. 2
   温度The contents were heated to and
3. 3
   温度maintained
4. 4
   温度at reflux under nitrogen for 12 hours
5. 5
   その他transferred to a separatory funnel
6. 6
   洗浄washed with water and brine
7. 7
   乾燥dried over magnesium sulfate
8. 8
   ろ過filtered
9. 9
   濃縮concentrated
10. 10
    その他to afford an oil
11. 11
    温度cooled in an ice bath
12. 12
    workup.STIRRINGwhile stirring
13. 13
    その他to precipitate solids
14. 14
    ろ過The solids were filtered
15. 15
    workup.DISSOLUTIONdissolved in ether
16. 16
    温度cooled in an ice bath
17. 17
    workup.STIRRINGstirred while saturated sodium bicarbonate
18. 18
    workup.ADDITIONwas added slowly until basic
19. 19
    その他The contents were transferred to a separatory funnel
20. 20
    洗浄washed with brine
21. 21
    乾燥dried over magnesium sulfate
22. 22
    ろ過filtered
23. 23
    濃縮concentrated

実験手順

In a 500-mL flask equipped with a septum inlet, magnetic stirring bar, and condenser leading to a mercury bubbler was placed 22.8 g (0.12 mol) of [2-(aminomethyl)4-(trifluoromethyl)phenyl]amine in 218 mL dimethoxyethane. To this reaction flask with stirring was added 26 mL (0.24 mol) N-methylmorpholine and 24 mL (0.13 mol) 3,5-bis(trifluoromethyl)benzyl bromide. The contents were heated to and maintained at reflux under nitrogen for 12 hours. Afterwards, TLC analysis revealed a minor amount of starting material remaining. The contents were cooled to room temperature, diluted with ether and transferred to a separatory funnel and washed with water and brine, dried over magnesium sulfate, filtered and concentrated to afford an oil. The oil was dissolved in hexane, cooled in an ice bath and acetic acid was added slowly while stirring to precipitate solids. The solids were filtered, dissolved in ether, and cooled in an ice bath and stirred while saturated sodium bicarbonate was added slowly until basic. The contents were transferred to a separatory funnel and washed with brine, dried over magnesium sulfate, filtered, and concentrated to give 12 g [2-amino-5-(trifluoromethyl)benzyl][3,5-bis(trifluoromethyl)benzyl]amine as an orange oil. In addition the hexane mother liquor contained significant amounts of product and byproducts. This liquor was concentrated to yield dark yellow oil that was used without further purification in the following step.

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