反応 #731297

反応方程式

1-chloro-6-iodohexane

2,2′-bithiophene

n-butyllithium

→

5-(6-chlorohexyl)-2,2′-bithiophene

収率 54.3%

溶媒

THF

反応条件

後処理

1. 1
   workup.ADDITIONAfter complete addition
2. 2
   その他The reaction was quenched with sat. aq. NH4Cl
3. 3
   抽出the reaction mixture was extracted with ethyl acetate (3×100 ml)
4. 4
   洗浄The combined organic extracts were washed with water, brine
5. 5
   乾燥dried over sodium sulphate
6. 6
   その他The solvent was removed under reduced pressure
7. 7
   その他the residue was purified by column chromatography on silica
8. 8
   洗浄eluting with petroleum ether

実験手順

To a stirred solution of 2,2′-bithiophene (10.0 g, 60.24 mmol) in anhydrous THF (150 ml) was added n-butyllithium (2.5 M in hexanes, 20.0 ml, 50.0 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 1-chloro-6-iodohexane (14.55 g, 50.0 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with sat. aq. NH4Cl, and the reaction mixture was extracted with ethyl acetate (3×100 ml). The combined organic extracts were washed with water, brine, and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica, eluting with petroleum ether, to give 5-(6-chlorohexyl)-2,2′-bithiophene as a white solid (7.73 g, 54%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.14 (d, J=5.3 Hz, 1.3 Hz, 1H, Ar—H), 7.08 (dd, J=3.5 Hz, 1.1 Hz, 1H, Ar—H), 6.97 (m, 2H, Ar—H), 6.66 (d, J=3.5 Hz, 1H, Ar—H), 3.51 (d, J=6.6 Hz, 2H, ClCH2), 2.78 (t, J=7.1 Hz 2H, ArCH2), 1.61-1.81 (m, 4H, CH2), 1.35-1.51 (m, 4H, CH2); MS (m/e): 282 (M+, 2%), 166 (8), 123 (39), 110 (22), 97 (100).

出典