反应 #2126564

反应方程式

8-(4-Bromophenyl)-1,4-dioxaspiro(4.5)dec-7-ene

4-ethoxy-2,3-difluorophenylboronic acid

potassium phosphate

1,4-dioxane

→

8-(4′-ethoxy-2′,3′-difluoro-(1,1′-biphenyl)-4-yl)-1,4-dioxaspiro(4.5)decane

收率 75.7%

溶剂

water

反应条件

后处理

1. 1
   温度heated
2. 2
   温度to reflux for 2 hours
3. 3
   萃取the aqueous layer was extracted with toluene
4. 4
   洗涤The combined organic layers were washed with water
5. 5
   干燥dried over anhydrous magnesium sulfate
6. 6
   浓缩The solution was concentrated under reduced pressure
7. 7
   其他the residue was purified by column chromatography with toluene as an eluent
8. 8
   workup.ADDITIONPd/C (1.5 g) was added to the purified product
9. 9
   其他Pd/C was removed
10. 10
    workup.DISTILLATIONsolvent was distilled off
11. 11
    其他The residue was purified by column chromatography with toluene as an eluent
12. 12
    其他silica gel as a stationary phase powder, and then by recrystallization from a mixed solvent of toluene and heptane (toluene:heptane=1:1 by volume)

实验过程

8-(4-Bromophenyl)-1,4-dioxaspiro(4.5)dec-7-ene (s71) (30.0 g), 4-ethoxy-2,3-difluorophenylboronic acid (s70) (24.6 g), potassium phosphate (K3PO4; 64.7 g), dichlorobistriphenylphosphine palladium (II) (Pd(Ph3P)2Cl2; 2.1 g) and 1,4-dioxane (300 ml) were placed in a reaction vessel under an atmosphere of nitrogen, and heated to reflux for 2 hours. After the reaction mixture had been cooled to 25° C., it was treated with water, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography with toluene as an eluent and silica gel as a stationary phase powder. Pd/C (1.5 g) was added to the purified product, and the mixture was stirred at room temperature under a hydrogen atmosphere until hydrogen absorption had ceased. After the reaction had been completed, Pd/C was removed, and then solvent was distilled off. The residue was purified by column chromatography with toluene as an eluent and silica gel as a stationary phase powder, and then by recrystallization from a mixed solvent of toluene and heptane (toluene:heptane=1:1 by volume) to give 8-(4′-ethoxy-2′,3′-difluoro-(1,1′-biphenyl)-4-yl)-1,4-dioxaspiro(4.5)decane (s72) (28.8 g). The yield based on the compound (s71) was 75.7%.

来源