反応 #717741

反応方程式

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

hydrochloric acid

5,9-Dibromo-7,7-dioctyl-7H-benzo[c]fluorene

n-butyllithium

→

2-(9-Bromo-7,7-dioctyl-7H-benzo[c]fluoren-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane

溶媒

tetrahydrofuran

methanol

diethylether

tetrahydrofuran

hexane

反応条件

後処理

1. 1
   workup.STIRRINGfurther stirred at −78° C. for one hour
2. 2
   その他the water layer was removed from the organic layer
3. 3
   workup.ADDITIONTo the organic layer, 1170 mL of distilled water was added
4. 4
   workup.STIRRINGstirred
5. 5
   その他Thereafter, the water layer was removed
6. 6
   workup.ADDITIONa 5% aqueous sodium hydrogen carbonate solution (1170 mL) was added
7. 7
   workup.STIRRINGstirred
8. 8
   その他Thereafter, the water layer was removed
9. 9
   workup.DISTILLATIONAfter distilled water (1170 mL)
10. 10
    workup.ADDITIONwas added
11. 11
    workup.STIRRINGstirred
12. 12
    その他the water layer was removed
13. 13
    濃縮Concentration and dehydration
14. 14
    その他to obtain an oily substance
15. 15
    その他to obtain a solid substance as a precipitate
16. 16
    ろ過which was filtrated
17. 17
    その他dried
18. 18
    その他Further, the solid substance was recrystallized from tetrahydrofuran and methanol

実験手順

Under an inert atmosphere, 70.00 g (0.117 mol) of 5,9-Dibromo-7,7-dioctyl-7H-benzo[c]fluorene (M-15) was dissolved in dehydrated tetrahydrofuran (1170 mL) and dehydrated diethylether (1170 mL). To the obtained solution, 73 mL (1.6 mol/L) of a hexane solution of n-butyllithium was added dropwise at −70° C. for 30 minutes and further stirred at −70° C. for 50 minutes. Subsequently, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise at −78° C. for 10 minutes and further stirred at −78° C. for one hour. To this solution, an aqueous hydrochloric acid solution was added dropwise at room temperature for 15 minutes and the water layer was removed from the organic layer. To the organic layer, 1170 mL of distilled water was added and stirred. Thereafter, the water layer was removed and a 5% aqueous sodium hydrogen carbonate solution (1170 mL) was added and stirred. Thereafter, the water layer was removed. After distilled water (1170 mL) was added and stirred, the water layer was removed. Concentration and dehydration were performed to obtain an oily substance. The oily product was dissolved in tetrahydrofuran. To this, methanol was added to obtain a solid substance as a precipitate, which was filtrated and dried. Further, the solid substance was recrystallized from tetrahydrofuran and methanol, twice to obtain a desired compound 2-(9-Bromo-7,7-dioctyl-7H-benzo[c]fluoren-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (M-14) (57.7 g) in a yield of 76%.

出典