Reaktion #67391

Reaktionsgleichung

Methylene chloride

fluorene

n-butyllithium

bromoacetaldehyde diethylacetal

→

Fluorenyl Acetaldehyde Diethylacetal

Lösungsmittel

diethyl ether

—

hexanes

diethyl ether

Reaktionsbedingungen

Aufarbeitung

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

Vorschrift

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.

Quelle