反応 #45528

反応方程式

benzophenone

n-butyl lithium hexane

hexamethyl phosphoramide

hydrochloric acid

3-tert-butyl-1-methyl-cyclopentadiene

→

aimed compound

3-tert-butyl-1-methyl-6,6-diphenyl fulvene

溶媒

tetrahydrofuran

tetrahydrofuran

Diethyl ether

反応条件

後処理

1. 1
   その他In a 200 ml three-necked flask equipped with a magnetic stirrer chip and three-way cock
2. 2
   workup.STIRRINGstirred at room temperature for 1 hr
3. 3
   その他To the solution, a solution prepared
4. 4
   workup.ADDITIONwas gradually added dropwise in an ice bath
5. 5
   workup.STIRRINGstirred at room temperature over night
6. 6
   workup.ADDITIONwas gradually added dropwise in an ice bath
7. 7
   workup.STIRRINGstirred at room temperature for some time
8. 8
   その他to separate an organic phase
9. 9
   洗浄The organic phase was washed with a saturated sodium bicarbonate aqueous solution, water and saturated brine
10. 10
    乾燥The organic phase was dried with anhydrous magnesium sulfate
11. 11
    ろ過the drying agent was filtered off
12. 12
    workup.DISTILLATIONthe solvent was distilled off from the filtrate under reduced pressure
13. 13
    その他to give a dark-red liquid
14. 14
    その他The liquid was purified with a column chromatography
15. 15
    workup.DISTILLATIONthe developing solvent was distilled off under reduced pressure

実験手順

In a 200 ml three-necked flask equipped with a magnetic stirrer chip and three-way cock thoroughly purged with nitrogen, 2.73 g of 3-tert-butyl-1-methyl-cyclopentadiene (20.1 mmol) was dissolved in 30 ml of dehydrated tetrahydrofuran in a nitrogen atmosphere. To the solution, 13.5 ml of n-butyl lithium/hexane solution (1.58M: 21.3 mmol) was gradually added dropwise in an ice bath and stirred at room temperature for 3 days. To the reaction solution, 10.5 ml of hexamethyl phosphoramide (60.4 mmol) was added and stirred at room temperature for 1 hr. To the solution, a solution prepared by dissolving 3.87 g of benzophenone (21.2 mmol) in 40 ml of dehydrated tetrahydrofuran was gradually added dropwise in an ice bath and stirred at room temperature over night. To the resulting reaction mixture, 50 ml of a hydrochloric acid aqueous solution (1N) was gradually added dropwise in an ice bath and stirred at room temperature for some time. Diethyl ether was added to the mixed solution to separate an organic phase. The organic phase was washed with a saturated sodium bicarbonate aqueous solution, water and saturated brine. The organic phase was dried with anhydrous magnesium sulfate, thereafter the drying agent was filtered off and the solvent was distilled off from the filtrate under reduced pressure to give a dark-red liquid. The liquid was purified with a column chromatography using 300 g of silica gel (developing solvent: n-hexane) and the developing solvent was distilled off under reduced pressure, and thereby the aimed compound was obtained in an amount of 3.28 g (10.9 mmol) as a reddish-orange solid (yield: 54%).

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