反応 #338894

反応方程式

magnesium

5-(1-adamantyl)-2-bromotoluene

4-(1-adamantyl)-bromobenzene

hydrochloric acid

→

4,4′-di(1-adamantyl)-2-methyl-1,1′-biphenyl

収率 79.0%

溶媒

tetrahydrofuran

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   workup.ADDITIONwere charged
2. 2
   温度refluxed under a nitrogen atmosphere for two hours
3. 3
   workup.ADDITIONwas added
4. 4
   温度under nitrogen flow and the mixture was refluxed for 12 hours
5. 5
   温度the mixture was refluxed for 30 minutes
6. 6
   その他After an aqueous layer was separated
7. 7
   その他removed
8. 8
   洗浄the reaction solution was washed with 200 mL of saturated sodium hydrogencarbonate aqueous solution
9. 9
   その他followed by removal of solvent under reduced pressure
10. 10
    その他Solid thus obtained

実験手順

In a 1 L recovery flask, 3.19 g of magnesium (131 mmol), g of 5-(1-adamantyl)-2-bromotoluene (131 mmol), 200 mL of tetrahydrofuran and a stirrer were charged and refluxed under a nitrogen atmosphere for two hours to prepare a Grignard reagent. Next, in another 1 L recovery flask, 38.2 g of 4-(1-adamantyl)-bromobenzene (131 mmol), 9.19 mg of bis(triphenylphosphine)palladium dichloride (13.1 mmol), 300 mL of tetrahydrofuran and a stirrer were charged. A tetrahydrofuran solution, which is the above-prepared Grignard reagent, was added thereto under nitrogen flow and the mixture was refluxed for 12 hours. Then, 60 mL of 10% hydrochloric acid aqueous solution was added thereto and the mixture was refluxed for 30 minutes. After an aqueous layer was separated and removed therefrom, the reaction solution was washed with 200 mL of saturated sodium hydrogencarbonate aqueous solution, followed by removal of solvent under reduced pressure. Solid thus obtained was refined by alumina column chromatography, thus obtaining 45.1 g of 4,4′-di(1-adamantyl)-2-methyl-1,1′-biphenyl (103.5 mmol; yield: 79.0%).

出典