反応 #67392

反応方程式

Methylene chloride

indene

n-butyllithium

bromoacetaldehyde diethylacetal

→

Indenyl Acetaldehyde Diethylacetal

溶媒

diethyl ether

—

hexanes

diethyl ether

反応条件

後処理

1. 1
   workup.ADDITIONThis yellow solution was added dropwise to
2. 2
   温度after warming to 25° C.
3. 3
   その他The solvent was then removed in vacuo
4. 4
   その他leaving brown oil
5. 5
   その他to give a cloudy white mixture which
6. 6
   抽出was extracted with deionized water (3×100 mL)
7. 7
   乾燥The brown organic layer was dried over Na2SO4
8. 8
   その他solids were separated by filtration
9. 9
   その他Solvent was removed from the filtrate in vacuo
10. 10
    その他resulting in brown oil

実験手順

A solution of n-butyllithium (20.0 mL, 1.6 M, 32.2 mmol) in hexanes was added dropwise to a cooled (0° C.) solution of indene (5.35 g, 32.2 mmol) in 50 mL of diethyl ether. The reaction solution turned yellow and was warmed to 25° C. for 30 minutes. This yellow solution was added dropwise to a cooled (0° C.) solution of bromoacetaldehyde diethylacetal (5.00 mL, 32.2 mmol) in 50 mL of diethyl ether. The reaction mixture turned bright red after warming to 25° C. and was stirred for 12 hours, during which time it darkened to brown. The solvent was then removed in vacuo leaving brown oil. Methylene chloride (100 mL) was added to give a cloudy white mixture which was extracted with deionized water (3×100 mL). The brown organic layer was dried over Na2SO4 and then solids were separated by filtration. Solvent was removed from the filtrate in vacuo resulting in brown oil. Yield: 5.48 g, 23.5 mmol (85%). 1H NMR (CDCl3, 600 MHz): δ 7.43 (d, 3JHH=7.2 Hz, 1H, H4), 7.35 (d, 3JHH=7.8 Hz, 1H, H7), 7.25 (t, 3JHH=7.2 Hz, 1H, H5), 7.19 (t, 3JHH=7.2 Hz, 1H, H6), 6.80 (dd, 1H, H2), 6.61 (dd, 1H, H3), 4.68 (m, 1H, CH), 3.69 (dm, 2H, OCH2CH3), 3.56 (m, 1H, H1), 3.52 (dm, 2H, OCH2CH3), 2.22 (m, 1H, CH2), 1.71 (m, 1H, CH2), 1.24 (t, 3JHH=7.2 Hz, 3H, OCH2CH3), 1.19 (t, 3JHH=7.2 Hz, 3H, OCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): 147.51 (s, C7a), 144.13 (s, C3a), 139.13 (s, C3), 130.79 (s, C2), 126.56 (s, C5), 124.73 (s, C6), 123.00 (s, C4), 121.05 (s, C7), 102.10 (s, CH), 61.44 (s, OCH2CH3), 61.23 (s, OCH2CH3), 46.66 (s, C1), 35.51 (s, CH2), 15.38 (s, OCH2CH3). MS (ES) m/z (assignment, relative intensity): 255.2 (C15H20O2Na, [M+Na]+, 100%). Anal. Calcd. for C15H20O2: C, 77.54; H, 8.68. Found: C, 77.34; H, 8.76.

出典