反应 #11284

反应方程式

2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

n-Butyllithium

acetone dry ice

4-bromo-N,N-diphenylaniline

→

N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

收率 72.8%

溶剂

THF

反应条件

后处理

1. 1
   workup.WAITwas continued at −78° C. for an hour
2. 2
   workup.WAITat −50° C. for an hour
3. 3
   温度The temperature was maintained at −78° C. for three hours
4. 4
   其他The cooling bath was removed
5. 5
   workup.WAITthe reaction left
6. 6
   温度to warm to room temperature
7. 7
   workup.ADDITIONThe reaction mixture was poured into saturated ammonium acetate
8. 8
   萃取extracted with ether
9. 9
   干燥The ether layer was dried over magnesium sulfate
10. 10
    浓缩concentrated
11. 11
    其他to give a viscous oil
12. 12
    其他Purification
13. 13
    温度by column chromatography (silica gel eluting with hexane:toluene mixtures of increasing gradient from 100% hexane to 40% hexane)

实验过程

n-Butyllithium was added dropwise via syringe to a −78° C. (acetone-dry ice cooling bath) solution of 4-bromo-N,N-diphenylaniline (24 g, 0.074 mole) in 175 ml dry THF. Stirring was continued at −78° C. for an hour and then at −50° C. for an hour. The mixture was cooled to −78° C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17.22 g, 0.0925 mole) added via syringe in one portion. The temperature was maintained at −78° C. for three hours. The cooling bath was removed and the reaction left to warm to room temperature while standing for 12 hours. The reaction mixture was poured into saturated ammonium acetate and extracted with ether. The ether layer was dried over magnesium sulfate and concentrated to give a viscous oil. Purification by column chromatography (silica gel eluting with hexane:toluene mixtures of increasing gradient from 100% hexane to 40% hexane) gave N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline as an oil (19.9 g, 72.8% yield), which slowly crystallized to a solid on standing.

来源