反応 #67391

反応方程式

Methylene chloride

fluorene

n-butyllithium

bromoacetaldehyde diethylacetal

→

Fluorenyl Acetaldehyde Diethylacetal

溶媒

diethyl ether

—

hexanes

diethyl ether

反応条件

後処理

1. 1
   workup.ADDITIONThe orange solution was added dropwise to
2. 2
   その他the solvent then removed in vacuo
3. 3
   その他leaving purple oil
4. 4
   その他to give a cloudy white mixture, which
5. 5
   抽出was extracted with deionized water (5×100 mL)
6. 6
   乾燥The yellow organic layer was dried over Na2SO4
7. 7
   その他the solids were then separated by filtration
8. 8
   その他Solvent was removed from the filtrate in vacuo
9. 9
   その他to leave a pale yellow oil which

実験手順

A solution of n-butyllithium (100.0 mL, 1.6 M, 0.161 mol) in hexanes was added dropwise to a cooled (0° C.) solution of fluorene (26.75 g, 0.161 mol) in 200 mL of diethyl ether. The reaction solution turned orange and was warmed to 25° C. for 30 minutes. The orange solution was added dropwise to a cooled (0° C.) solution of bromoacetaldehyde diethylacetal (25.0 mL, 0.161 mol) in 50 mL of diethyl ether. The reaction solution was stirred for 12 hours and the solvent then removed in vacuo leaving purple oil. Methylene chloride (300 mL) was added to the residue to give a cloudy white mixture, which was extracted with deionized water (5×100 mL). The yellow organic layer was dried over Na2SO4 and the solids were then separated by filtration. Solvent was removed from the filtrate in vacuo to leave a pale yellow oil which solidified to a yellow waxy solid upon standing. Yield: 42.2 g, 0.149 mol (93%). 1H NMR (CDCl3, 600 MHz): δ 7.73 (d, 3JHH=7.8 Hz, 2H, flu-H4), 7.54 (d, 3JHH=7.8 Hz, 2H, flu-H1), 7.34 (t, 3JHH=7.2 Hz, 2H, flu-H3), 7.28 (t, 3JHH=7.2 Hz, 2H, flu-H2), 4.69 (t, 3JHH=6.0 Hz, 1H, CH), 4.08 (t, 3JHH=7.2 Hz, 1H, flu-CH), 3.52 (dm, 4H, OCH2CH3), 2.21 (dd, 2H, CH2), 1.13 (t, 3JHH=7.2 Hz, 6H, OCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): 147.25 (s, C1-a), 140.81 (s, C4a), 126.96 (s, C2), 126.82 (s, C3), 124.73 (s, C1), 119.78 (s, C4), 101.41 (s, CH), 61.45 (s, OCH2CH3), 43.93 (s, C9), 37.49 (s, CH2), 15.27 (s, OCH2CH3). MS (ES) m/z (assignment, relative intensity): 305.2 (C19H22O2Na, [M+Na]+, 100%). Anal. Calcd. for C19H22O2: C, 80.82; H, 7.85. Found: C, 80.89; H, 8.09.

出典